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Im Rahmen dieser Dissertation wurden insgesamt drei verschiedene Fragestellungen an biologisch relevanten Modellsystemen mit Hilfe von diversen linearen und nichtlinearen Raman-spektroskopischen Techniken bearbeitet. Neben der Untersuchung von Wasserstoffbrücken-gebundenen Komplexen und ihrer Dynamik auf der fs-Zeitskala (Kapitel 4) bildeten Untersuchungen zur Struktur von Porphyrinen (Kapitel 5) und beta-Carotin (Kapitel 6) als Vertreter wichtiger Klassen von Biomolekülen den Schwerpunkt dieser Arbeit. Die spektroskopischen Ergebnisse wurden durchweg über Strukturen und Schwingungsspektren, welche mit Hilfe der Dichtefunktionaltheorie (DFT) berechnet wurden, unterstützt. Die dritte bearbeitete Thematik zum Nachweis anthropogener und ökologisch relevanter Aerosole war bioanalytisch motiviert und wurde anhand von Pestizid-Modellsubstanzen bearbeitet (Kapitel 7).
Iodine oxides appear as reactive intermediates in atmospheric chemistry. Here, we investigate IO and HOI by mass‐selective threshold photoelectron spectroscopy (ms‐TPES), using synchrotron radiation. IO and HOI are generated by photolyzing iodine in the presence of ozone. For both molecules, accurate ionization energies are determined, 9.71±0.02 eV for IO and 9.79±0.02 eV for HOI. The strong spin‐spin interaction in the 3Σ− ground state of IO+ leads to an energy splitting into the Ω=0 and Ω=±1 sublevels. Upon ionization, the I−O bond shortens significantly in both molecules; thus, a vibrational progression, assigned to the I−O stretch, is apparent in both spectra.
Using Photoionization to Investigate Reactive Boron Species and the Kinetics of Hydrocarbon Radicals
(2021)
This thesis highlights the importance of isomer-selective approaches for the complete analysis of chemical processes. The method of choice is photoelectron/photoion coincidence spectroscopy, which allows simultaneous detection of electrons and ions coming from a single ionization event. Ionization techniques are sensitive and can record multiple species simultaneously, rendering them ideal tools to probe molecular transformations. Coupling these setups to synchrotron radiation allows one to analyze complex mixtures with isomer selectivity, based on ionization energies and vibrational structure in the cation, without any prior separation steps. Only few setups exist that can be used to gather these data, although their impact and applicability is growing steadily in various fields. For closed-shell species an easier and more widely used method is gas-chromatography, but most open shell species would not survive the separation process. Due to the reactivity of radicals they have to be created by selectively converting stable precursor molecules. Depending on the radical generation method different properties can be investigated ranging from thermodynamic data, over concentrations in high temperature environments, to chemical kinetics.
The first part of this thesis deals with the determination of bimolecular rate constants. Isomeric hydrocarbon radicals were generated by a high intense UV light pulses and their kinetics with oxygen was measured. The pressure dependence of different isomers in the falloff region was compared to theoretical models, and their reactivity could be explained.
The second part deals with boron containing compounds in various electronic situations. The corresponding precursors were successfully synthesized or could be bought. They were subjected to fluorine atoms in chemical reactors or destroyed pyrolytically at high temperatures. Most investigated species exhibited vibronic effects that could be elucidated using high level computations.
Within this work, an additive and a subtractive QM/MM interface were implemented into CAST. The interactions between QM and MM system are described via electrostatic embedding. Link atoms are used to saturate dangling bonds originating from the separation of QM and MM system. Available energy evaluation methods to be combined include force fields (OPLSAA and AMBER), semi-empirical programs (Mopac and DFTB+), and quantum-chemical methods (from Gaussian, Orca, and Psi4). Both the additive and the subtractive interface can deal with periodic boundary conditions. The subtractive scheme was extended to enable QM/QM, three-layer, and multi-center calculations. Another feature only available within the subtractive interface is the microiteration procedure for local optimizations.
The novel QM/MM methods were applied to the investigation of the reaction path for the complex formation between rhodesain and K11777. Benchmark calculations show a very good agreement with results from Gaussian-ONIOM. When comparing the relative energies obtained with different options to a computation where the whole system was treated with the “QM method” DFTB3, the electrostatic embedding scheme with option “delM3” gives the best results. “delM3” means that atoms with up to three bonds distance to the QM region are ignored when creating the external charges. This is done in order to avoid a double counting of Coulomb interactions between QM and MM system. The embedding scheme for the inner system in a three-layer calculation, however, does not have a significant influence on the energies. The same is true for the choice of the coupling scheme: Whether the additive or the subtractive QM/MM interface is applied does not alter the results significantly. The choice of the QM region, though, proved to be an important factor. As can be seen from the comparison of two QM systems of different size, bigger is not always better here. Instead, one has to make sure not to separate important (polar) interactions by the QM/MM border.
After this benchmark study with singlepoint calculations, the various possibilities of CAST were used to approximate the solution of a remaining problem: The predicted reaction energy for the formation of the rhodesain-K11777 complex differs significantly depending on the starting point of the reaction path.
The reason for this is assumed to be an inadequate adjustment of the environment during the scans, which leads to a better stabilization of the starting structure in comparison to the final structure. The first approach to improve this adjustment was performing the relaxed scan with a bigger QM region instead of the minimal QM system used before. While the paths starting from the covalent complex do not change significantly, those starting from the non-covalent complex become more exothermic, leading to a higher similarity of the two paths. Nevertheless, the difference of the reaction energy is still around 15 kcal/mol, which is far from a perfect agreement. For this reason, Umbrella Samplings were run. Here, the adjustment of the environment is not done by local optimizations like in the scans, but by MD simulations. This has the advantage that the system can cross barriers and reach different local minima. The relative free energies obtained by Umbrella Samplings with suitable QM regions are nearly identical, independently of the starting point of the calculation. Thus, \(\Delta A\) evaluated by these computations can be assumed to reproduce the real energy change best. An MD simulation that was started from the transition state in order to mimic a “real-time” reaction indicates a very fast adjustment of the environment during the formation of the complex. This confirms that Umbrella Sampling is probably better suitable to describe the reaction path than a scan, where the environment can never move strong enough to leave the current local minimum.
cAAC‐Stabilized 9,10‐diboraanthracenes—Acenes with Open‐Shell Singlet Biradical Ground States
(2020)
Narrow HOMO–LUMO gaps and high charge‐carrier mobilities make larger acenes potentially high‐efficient materials for organic electronic applications. The performance of such molecules was shown to significantly increase with increasing number of fused benzene rings. Bulk quantities, however, can only be obtained reliably for acenes up to heptacene. Theoretically, (oligo)acenes and (poly)acenes are predicted to have open‐shell singlet biradical and polyradical ground states, respectively, for which experimental evidence is still scarce. We have now been able to dramatically lower the HOMO–LUMO gap of acenes without the necessity of unfavorable elongation of their conjugated π system, by incorporating two boron atoms into the anthracene skeleton. Stabilizing the boron centers with cyclic (alkyl)(amino)carbenes gives neutral 9,10‐diboraanthracenes, which are shown to feature disjointed, open‐shell singlet biradical ground states.
Im Rahmen der vorliegenden Arbeit wurde durch einzelmolekülspektroskopischer bzw. -mikroskopischer Methoden in Kombination mit einer mikrofluischen Zel- le unter Potenzialkontrolle die Elektrochemie von einzelnen einwandigen (6,5)- Kohlenstoffnanoröhren untersucht. Hierfür wurde ein Nahinfrarot-Photolumineszenz- Mikroskop aufgebaut und eine speziell an die experimentellen Vorgaben angepasste elektrochemische Zelle entwickelt, insofern als drei Elektroden (Arbeits-, Gegen- und Referenzelektrode) in einen mikrofluidischen Chip integriert wurden. Darüber hinaus war für die Durchführung der Experimente unter Wasser- und Sauerstoffaus- schluss die Konstruktion eines Handschuhkastens notwendig, sowie eine allgemeine Vorbehandlung der Elektrolytlösungen zur Entfernung gelöster Gase und Wasserreste.
Ein weiteres Projekt umfasste den Aufbau einer chemischen Gasphasenabschei- dungsapparatur zur Synthese von Kohlenstoffnanoröhren. Die hierbei durchgeführten Experimente erbrachten Klarheit über den Einfluss der Prozessparameter Druck, Temperatur und Durchflussrate an Edukten.
Aus den PL-Intensitätsänderungen bei Potenzialvariation konnten Reduktions- und Oxidationspotenziale (ERed = 0.15 V; EOx = 1.34 V) einzelner (6,5)-SWNTs gegen- über einer Platin Referenzelektrode und einem daraus resultierenden Redoxpotenzial
von ∆ERedOx = 1.19 V ermittelt werden. Durch diese einzelmolekülspektroskopische
Methode konnte zum einen gewährleistet werden, dass nur dieser spezielle Chira- litätstyp untersucht wurde und zum anderen eine Verfälschung der Resultate durch einen Potenzialabfall wie er typischerweise in CNT-Filmen auftritt aussgeschlossen werden. Eine Kombination der PL-Daten mit der Ramanintensitätsabhängigkeit des (6,5)-SWNT-S2-Übergangs bei Potenzialvariation erlaubte eine genauere Analyse des Löschmechanismus der PL von Kohlenstoffnanoröhren. Mithilfe eines von Her- tel et al. entwickelten diffusionslimitierten Stoßdesaktivierungsmodells konnte eine invers-quadratische Proportionalität zwischen der (6,5)-SWNT-Emission und den spannungsinduzierten Ladungsträgern ausgemacht werden. Auf Grundlage dieses Ergebnisses folgt, dass die über Photolumineszenzänderungen ermittelten Reduktions-und Oxidationswerte nicht mit den Bandkanten der CNTs übereinstimmen müssen, und dass für deren Bestimmung vielmehr auf Raman- bzw. Absorptionsspektroskopi- sche Techniken zurückgegriffen werden muss.
Die einzelmolekülspektroskopische Herangehensweise ermöglichte ferner eine statis- tische Analyse der Verteilung der Reduktions- und Oxidationspotenziale im Vergleich zu den jeweiligen Erwartungswerten. Hierdurch konnte eine Einteilung der Modifika- tionseinflüsse auf das SWNT-Redoxverhalten in zwei Grenzfälle erfolgen. Es wurde angenommen, dass diese als “Dispergiermitteleffekte” und “CNT-Strukturdefekte” be- zeichneten Auswirkungen entweder das Resultat einer heterodispersen Verteilung an DOC auf der CNT-Oberfläche oder eine Folge von Defekten in der CNT-Gitterstruktur waren. In diesem Zusammenhang ergab sich aus der interpartikulären Analyse der Reduktions- und Oxidationswerte eine Korrelation, die einem dominierenden Einfluss der “CNT-Strukturdefekte” zugeordnet werden konnte. Dieser Beobachtung entgegen- gesetzt konnten aber auch über Untersuchungen der Redoxpotenziale innerhalb einer (6,5)-SWNT lokale Bereiche ausgemacht werden, die eine signifikante Abhängigkeit von “Dispergiermitteleffekte” aufwiesen.
Abgesehen von diesen Einflüssen auf den Emissionsverlauf wurde auch eine Be- trachtung der Breite des spannungsgesteuerten Emissionsabfall durchgeführt. Da- raus konnte ermittelt werden, dass diese Ausdehnung eine Konsequenz aus der PL- Löschungseffizienz der Ladungsträger ist und, dass bei einer Verteilung von 0.32 Löschzentren pro Nanometer eine vollständige Abnahme der Photolumineszenzinten- sität induziert wird.
Darüber hinaus wurde im Rahmen dieser Arbeit das redoxchemische Verhalten in- dividueller (6,5)-SWNTs in Wechselwirkung mit Ferrocenmolekülen untersucht. Die erhaltenen Ergebnisse ließen annehmen, dass die sich ausbildende Verbindung nicht-kovalenter Natur ist. Zwei verschiedene Gründe führten zu dieser Erkennt- nis: einerseits ließen sich die Ferrocenmoleküle von der CNT-Oberfläche durch ein Durchspülen des mikrofluidischen Kanals mit einer reinen DMF-Lösung entfernen und andererseits war keine dauerhafte Emissionsminderung durch die Ausbildung kovalenter Bindungen zu beobachten. Aus der potenzialabhängigen PL wurde zudem ein Elektronentransfer der Ferrocenmoleküle in die optisch generierten Löcher des CNT-Valenzbandes festgestellt und über eine anregungsintensitätsabhängige Messung die Zunahme dieses Ladungstransfers bei steigendem Photonenfluss nachgewiesen.
Hinsichtlich der Anwendung von Kohlenstoffnanoröhren zur Elektrolyse bzw. Photo- lyse von Wasser wurde auch die Redoxchemie von (6,5)-SWNTs in diesem Solvens untersucht. Bezüglich der Emissionsintensität konnte gezeigt werden, dass diese im Vergleich zu organischen Lösungsmitteln reduziert vorliegt. Außerdem wurde eine irreversible Reaktion nach anodischer Polarisation über eine dauerhafte Löschung der PL beobachtet. Die Bestimmung der hierfür notwendigen Reaktionsumstände erbrachte, dass Wasser, Exzitonen (erzeugt durch optische Anregung) und spannungs- induzierte Löcher im Valenzband zur Bildung einer [SWNT(Q)]-Spezies führen, welche die irreversible Minderung der CNT-Emission verursacht. Darüber hinaus konnte die Reaktionsgeschwindigkeit über eine Kinetik pseudo-nullter-Ordnung be- schrieben werden, unter der Voraussetzung, dass die soeben genannten Parameter konstant verblieben. Desweiteren zeigte sich in einer ferrocenhaltigen Lösung, dass der Löscheffekt der [SWNT(Q)]-Spezies im anodischen Potenzialbereich teilweise reduziert wird. Es wurde angenommen, dass diese Beobachtung auf eine Oxidation der Löschzentren durch die Fc+-Kationen gründet.
Mit Hilfe der CVD-Apparatur gelang es Kohlenstoffnanoröhren zu synthetisieren, wobei Ethanol als Kohlenstoffquelle und ein Eisen-Kobalt-Zeolith-Gemenge als Ka- talysator diente. Die Analyse der verschiedenen Prozessparameter zeigte, dass bei T = 750 °C das beste Verteilungsverhältnis zwischen den gewünschten (6,5)-SWNTs und anderen CNT-Chiralitäten bzw. dem amorphen Kohlenstoff vorliegt. Hierfür war, dass bei T < 750 °C die Verbrennung unerwünschter amorpher Kohlenstoffreste nur geringfügig stattfindet, und dass bei T > 750 °C die Bildung anderer Chiralitäten mit größerem Durchmesser als die (6,5)-SWNT bevorzugt wurde. Die Variation der Durchflussrate hingegen wirkte sich nur in einer absoluten Zunahme aller Chirali- täten aus. Die Steigerung des (6,5)-SWNT-Anteils für höhere Durchflüsse gelang trotzdem durch die geschickte Auswahl geeigneter Druck- und Temperaturwerte. Die Experimente zur Untersuchung der Druckabhängigkeit wiesen auf eine Relation mit dem Gesetz von Le Chatelier hin, insofern als bei einer Druckverringerung eine Verschiebung der Ethanol-Crackreaktion auf Produktseite stattfand. In diesem Zusam- menhang wurde angenommen, dass die damit verstärkt gebildeten Moleküle Ethan, Ethen und Methan den CNT-Anteil zwar erhöhen, jedoch auch eine Steigerung der amorphen Kohlenstoffkonzentration verursachen. Dementsprechend ergab ein Druck von p = 9 mbar das beste (6,5)-SWNT zu dem amorphen Kohlenstoffverhältnis.
Anhand der Arbeiten in dieser Dissertation sind neue Erkenntnisse zwischen der PL-Sensitivität von (6,5)-SWNTs und deren Ladungszustand erhalten worden. Insbe- sondere die genaue Bestimmung der Korrelation zwischen der Photolumineszenz und den induzierten Ladungsträgern ermöglicht einen gezielteren Einsatz von Kohlenstoff- nanoröhren – so zum Beispiel im Bereich der Sensorik. In diesem Zusammenhang zeigen auch die interpartikulären Analysen der Redoxpotenzialverteilung die genau- en Auswirkungen vom Lösungsmittel und der Defektdichte auf die elektronische Struktur der CNTs auf. Darüber hinaus kann aus der Ursachenbestimmung für die Varianz der literaturbekannten Reduktions- bzw. Oxidationspotenziale fortan die ge- eignete spektroskopische Methode zur Evaluierung der Position von Leitungs- und Valenzband in Kohlenstoffnanoröhren besser eingegrenzt werden. Die spektroelektro- chemischen Analysen von (6,5)-SWNTs im Lösungsmittel Wasser und speziell die Bestimmung der Kinetik für die auftretende Reaktion liefern einen tieferen Einblick in die Wechselwirkung (6,5)-SWNT-H2O. Diese Ergebnisse sind insbesondere bei der Verwendung von Kohlenstoffnanoröhren als Elektrodenmaterial für die photolytische bzw. elektrolytische Spaltung von Wasser in Wasserstoff und Sauerstoff von Bedeu- tung. Neben der Untersuchung der SWNT-Wasser Interaktion unter andoischer und optischer Anregung, die zu einer kovalenten Bindung führte, wurde mit Hilfe der (6,5)- SWNT-Ferrocen Wechselwirkung ein Beispiel für eine nichtkovalente Redoxreaktion dargestellt, womit ein Vergleich dieser beiden Spezies und ihrer unterschiedlichen Auswirkungen auf die elektronische Struktur aufgezeigt werden konnte.
In dieser Arbeit werden Pflanzen, Pflanzengewebe, Pflanzenzellen und Mikro-organismen spektroskopisch untersucht und ihre Inhaltsstoffe unter minimaler Probenpräparation im biologischen Gewebe direkt lokalisiert und identifiziert. Unter den verfügbaren Schwingungs-spektroskopischen Methoden ist die Mikro-Raman-Spektroskopie für diese Fragestellungen besonders gut geeignet, da Wasser Raman-Spektren nur wenig beeinflusst. Daher kann mit Raman-spektroskopischen Methoden auch in stark wasserhaltigem Gewebe gemessen werden. Weiterhin erhält man mit der Mikro-Raman-Spektroskopie eine gute räumliche Auflösung im sub-µm-Bereich, wodurch es möglich ist, heterogene Proben zu untersuchen. Darüber hinaus kann die Mikro-Raman-Spektroskopie mit anderen Methoden, wie z. B. der oberflächenverstärkten Raman-Spektroskopie (SERS), kombiniert werden. In pflanzlichen Zellen liegt eine Vielzahl von Substanzen in geringen Konzentrationen vor. Aufgrund der niedrigen Quantenausbeute des Raman-Effekts treten vor allem Substanzen, die eine Resonanz-Verstärkung erfahren, in den Spektren hervor. Diese Substanzen, wie z. B. b-Carotin, können deshalb in geringen Konzentrationen detektiert werden. Der Schwerpunkt dieser Arbeit liegt in der Untersuchung von Sekundär-Metaboliten wie Alkaloiden, Lipiden oder Terpenen, die in der Pflanze agglomerieren. Neben der Identifikation von Inhaltsstoffen, können die Raman-Spektren von Pflanzen für die chemotaxonomische Klassifizierung mit Hilfe der hierarchischen Clusteranalyse verwendet werden. Die Identifizierung von Mikroorganismen auch in sehr geringen Mengen (Monolage, einzelne Zellen) ist mit der Mikro-Raman-Spektroskopie nur unter bestimmten Voraussetzungen durchführbar. Für weitergehende Untersuchungen wird hier die SERS-Sonde oder ein TERS-Aufbau verwendet werden.
The experimental technique predominantly employed within the scope of this Thesis constitutes one subarea of femtochemistry: the time-resolved spectroscopy of photoin-
duced chemical reactions in the liquid phase by means of molecular signatures in the mid-infrared (MIR) spectral range. Probing transient vibrational states, i.e., dynamic
changes in the vibrational motion of specic molecular subunits or functional Groups allows for a distinct separation and assignment of measured signals to emerging molecular species. For this purpose, one key building block is indispensable, which most of the investigations carried out within the eld of femtochemistry have in common: a coherent light source delivering ultrashort laser pulses with a temporal duration that matches the femtosecond time scale on which molecular motions typically occur. This instrumentation enables the observation of photoinduced chemical reactions from the
starting point|the excitation event to the appearance of intermediates to the nal formation of stable photoproducts after several pico- or nanoseconds.
This work comprises the acquisition and presentation of time-resolved spectroscopic data related to promising molecular systems upon photoexcitation as well as the im-
plementation and testing of experimental optical techniques both for the presented experiments but as well for experiments conceivable in the future. In addition, linear spectroscopy measurements and quantum-chemical simulations on the emerging chemical species have been carried out. In so doing, the primary processes and subse-
quently emerging reaction products of two compounds on a timescale of several nanoseconds after photoexcitation have been elucidated in great detail. Both compounds, the
[Mn(CO)3(tpm)]+ (tpm = tris(2-pyrazolyl)methane) CO-releasing molecule (CORM) and the 5-diazo Meldrum's acid (DMA), are of academic interest but in addition belong
to molecular classes that might be utilized in the near future as dark-stable prodrugs under physiological conditions or that are already utilized in industrial chemistry procedures, respectively. The ndings of both studies gave rise to implement and examine two techniques for prospective transient absorption experiments, namely the shaping and characterization of ultraviolet (UV) laser pulses and the recording of two-photon excitation spectra. Beyond that, since each of the depicted experiments is based on the detection of weak transient absorption signals in the MIR spectral region, two dif-
ferent detection schemes, via chirped-pulse upconversion (CPU) on the one hand and via direct multichannel MCT detection on the other hand, have been juxtaposed at the
conclusion of this work. Since both techniques are suitable in femtosecond pump-probe measurements but thereby exhibit individual strengths and weaknesses, a comparative study provides clarication of the respective pros and cons. The first study introduced within this work investigates the complex photochemistry
of DMA, a photoactive compound used in lithography and industrial chemistry. By femtosecond MIR transient absorption spectroscopy covering several nanoseconds, the
light-induced dynamics and ultrafast formation of several photoproducts from the manifold of reaction pathways have been disclosed to form a coherent picture of the overall
reaction scheme. After UV excitation of DMA dissolved in methanol to the second excited state S2, 70% of excited molecules relax back to the S0 ground state. In compet-
ing processes, they can either undergo an intramolecular Wolff rearrangement to form ketene, which reacts with a solvent molecule to an enol intermediate and further to carboxylate ester, or they rst relax to the DMA S1 state, from where they can isomerize to a diazirine. The third competing reaction channel, having the lowest quantum efficiency with respect to the rst two channels, is the formation of a singlet carbene out of the S1 state. From there an ylide can arise or, via an intersystem crossing, the triplet form of the carbene follows. Whereas the primary reaction steps occur on a picosecond timescale, the subsequently arising intermediates and stable photoproducts are formed
within a few hundreds to thousands of picoseconds. For a reliable identication of the involved compounds, density functional theory calculations on the normal modes and
Fourier-transform infrared spectroscopy of the reactant and the photoproducts in the chemical equilibrium accompany the analysis of the transient spectra. Additional experiments in ethanol and isopropanol led to slight spectral shifts as well as elongated time
constants due to steric hindrance in transient spectra connected with the ester Formation channel, further substantiating the assignment of the occurring reaction pathways and photoproducts.
The study demonstrated that the combination of linear and time-resolved spectroscopic measurements in conjunction with quantum-chemical calculations constitutes a powerful tool to unravel even highly complex photoreactions exhibiting multiple consecutive intermediate states within parallel reaction pathways. Although some of the individual reaction steps, for example the ketene formation via Wolff rearrangement, have been observed on ultrashort time scales before, this work encompassed the Observation of the whole set of appearing photoproducts of DMA in different alcohol solutions within several nanoseconds. In this sense, the ultrafast photochemistry of DMA represents a prototype example for a multisequential reaction scheme, elucidated by the capabilities of femtosecond MIR spectroscopy.
With a modified instrumentation concerning amongst others the system delivering the fundamental laser pulses or the generation of the UV pump pulses, the next ob-
jective within this work was to elucidate the primary processes upon UV Irradiation of a manganese tricarbonyl CORM in aqueous environment. The time-resolved
experiment was performed with two different pump wavelengths and furthermore supported by linear spectroscopy methods and time-dependent density functional theory (TDDFT) calculations on the excited states as well as DFT calculations on the ground
states. The measurements revealed that irradiating the compound with UV excitation pulses primarily leads to ultrafast photolysis of one CO ligand. Geminate recombination may occur within one picosecond but it remains a minor process as the photolyzed CO
group is liberated and the unoccupied coordination site is predominantly filled by an incoming solvent molecule. There was no evidence for hot CO bands, i.e., the remaining CO ligands|in the dicarbonyl photoproduct as well as in the intact CORM are not vibrationally excited through the UV excitation of the CORM. According to this, the excess energy merges into low-frequency vibrational modes associated with the molecule as a whole. Since studies on a macroscopic scale at irradiation times of several minutes prove that UV irradiation eventually leads to the release of two or even all three CO
ligands, further loss of CO most likely necessitates manganese oxidation or another interaction with light. To clarify the latter, a consecutive UV pulse was employed in order to excite the photoproducts subsequent to the initial pump interaction. However, the data obtained was not instructive enough to denitely exclude the manganese oxidation being responsible for the loss of further CO groups. Besides the exchange of a CO Group by a solvent molecule or the geminate recombination, the employment of two different excitation wavelengths in combination with ndings derived from the TDDFT calculations suggested another reaction process, namely the possibility that the excitation does not lead to any bond cleavage at all. As the CORM under investigation is tissue-selective and cytotoxic against cancer cells, knowledge of these rst photoinduced reaction steps is essential for a full understanding of its biological activity. Inspired by these two studies, experimental techniques for prospective transient absorption measurements have been implemented and tested within preparative measure-
ments. First, in the course of a UV-pump-MIR-probe experiment with specically tailored excitation pulses, one could pursue the aim of coherently controlling the outcome of a photoreaction in the liquid phase. Out of the rich photochemistry of DMA the vibrational signature of a particular molecular species might thereby serve as a feedback signal, which is a central part of a learning loop that adaptively determines the pulse shape that steers the quantum mechanical system upon photoexcitation into a desired direction. This motivated the installation and testing of devices by means of which the shaping and characterization of ultrashort laser pulses in the UV could be performed. Second, motivated by the biological applications of CORMs, one can imagine a scenario where a certain amount of CORMs is deposited inside cancerous tissue. Since the activation of CO loss by means of UV pulses is not possible due to the absorption characteristics of biological tissue, the simultaneous excitation via two photons from the visible spectral regime seems appealing. However, success or failure of such an application depends on whether the deposited compound efficiently absorbs two photons simultaneously, i.e., whether the two-photon absorption cross section is large enough. Therefore, a setup to record two-photon excitation spectra under full consideration of
the crucial laser pulse parameters like the pulse duration, energy and central wavelength was arranged and tested. The rst results were obtained with a commercially available reference system (Mn2CO10) but the setup as well as the described measurement and
data analysis procedure can easily be applied to record the two-photon absorption cross section of more promising molecular systems. Third, as the detection of probe pulses
in the MIR spectral region is part of each time-resolved measurement throughout this thesis, a comparison between the newly established technique of CPU and direct multi-
channel MCT detection is presented by means of pump{probe experiments on Mn2CO10 and Co4CO12 with a 1 kHz shot-to-shot data acquisition. It was shown that the CPU detection technique scores with its high spectral resolution and coverage of the easy-to-handle and more cost-effective CCD detectors. On the other hand, in the course of the additional nonlinear upconversion process intensity fluctuations of the chirped fundamental pulses are transferred to the probe spectrum in the visible regime. This entails a lower signal-to-noise ratio than the direct MCT detection, which can be compensated by an additional normalization procedure applied to the CPU probe pulses. As a consequence, the CPU detection scheme offers more flexibility for future investigations
employing MIR probe pulses. This is of great importance for many applications within the presented eld of femtochemistry as a huge variety of time-resolved investigations on a multitude of systems in the liquid phase is based on the detection of weak transient
absorption signals in the MIR spectral region.
The concepts of aromaticity and antiaromaticity have a long history, and countless demonstrations of these phenomena have been made with molecules based on elements from the p, d, and f blocks of the periodic table. In contrast, the limited oxidation‐state flexibility of the s‐block metals has long stood in the way of their participation in sophisticated π‐bonding arrangements, and truly antiaromatic systems containing s‐block metals are altogether absent or remain poorly defined. Using spectroscopic, structural, and computational techniques, we present herein the synthesis and authentication of a heterocyclic compound containing the alkaline earth metal beryllium that exhibits significant antiaromaticity, and detail its chemical reduction and Lewis‐base‐coordination chemistry.
Coherent two-dimensional (2D) optical spectroscopy has revolutionized our ability to probe many types of couplings and ultrafast dynamics in complex quantum systems. The dynamics and function of any quantum system strongly depend on couplings to the environment. Thus, studying coherent interactions for different environments remains a topic of tremendous interest. Here we introduce coherent 2D electronic mass spectrometry that allows 2D measurements on effusive molecular beams and thus on quantum systems with minimum system-bath interaction and employ this to identify the major ionization pathway of 3d Rydberg states in NO2. Furthermore, we present 2D spectra of multiphoton ionization, disclosing distinct differences in the nonlinear response functions leading to the ionization products. We also realize the equivalent of spectrally resolved transient-absorption measurements without the necessity for acquiring weak absorption changes. Using time-of-flight detection introduces cations as an observable, enabling the 2D spectroscopic study on isolated systems of photophysical and photochemical reactions.
Plasmonic modes supported by noble-metal nanostructures offer strong subwavelength electric-field confinement and promise the realization of nanometer-scale integrated optical circuits with well-defined functionality. In order to measure the spectral and spatial response functions of such plasmonic elements, we combine a confocal microscope setup with spectral interferometry detection. The setup, data acquisition, and data evaluation are discussed in detail by means of exemplary experiments involving propagating plasmons transmitted through silver nanowires. By considering and experimentally calibrating any setup-inherent signal delay with an accuracy of 1 fs, we are able to extract correct timing information of propagating plasmons. The method can be applied, e.g., to determine the dispersion and group velocity of propagating plasmons in nanostructures, and can be extended towards the investigation of nonlinear phenomena.
The reaction products of the picolyl radicals at high temperature were characterized by mass‐selective threshold photoelectron spectroscopy in the gas phase. Aminomethylpyridines were pyrolyzed to initially produce picolyl radicals (m /z =92). At higher temperatures further thermal reaction products are generated in the pyrolysis reactor. All compounds were identified by mass‐selected threshold photoelectron spectroscopy and several hitherto unexplored reactive molecules were characterized. The mechanism for several dissociation pathways was outlined in computations. The spectrum of m /z =91, resulting from hydrogen loss of picolyl, shows four isomers, two ethynyl pyrroles with adiabatic ionization energies (IE\(_{ad}\)) of 7.99 eV (2‐ethynyl‐1H ‐pyrrole) and 8.12 eV (3‐ethynyl‐1H ‐pyrrole), and two cyclopentadiene carbonitriles with IE′s of 9.14 eV (cyclopenta‐1,3‐diene‐1‐carbonitrile) and 9.25 eV (cyclopenta‐1,4‐diene‐1‐carbonitrile). A second consecutive hydrogen loss forms the cyanocyclopentadienyl radical with IE′s of 9.07 eV (T\(_0\)) and 9.21 eV (S\(_1\)). This compound dissociates further to acetylene and the cyanopropynyl radical (IE=9.35 eV). Furthermore, the cyclopentadienyl radical, penta‐1,3‐diyne, cyclopentadiene and propargyl were identified in the spectra. Computations indicate that dissociation of picolyl proceeds initially via a resonance‐stabilized seven‐membered ring.
Besides their widespread use in coordination chemistry, 2,2’‐bipyridines are known for their ability to undergo cis–trans conformational changes in response to metal ions and acids, which has been primarily investigated at the molecular level. However, the exploitation of such conformational switching in self‐assembly has remained unexplored. In this work, the use of 2,2’‐bipyridines as acid‐responsive conformational switches to tune supramolecular polymerization processes has been demonstrated. To achieve this goal, we have designed a bipyridine‐based linear bolaamphiphile, 1, that forms ordered supramolecular polymers in aqueous media through cooperative aromatic and hydrophobic interactions. Interestingly, addition of acid (TFA) induces the monoprotonation of the 2,2’‐bipyridine moiety, leading to a switch in the molecular conformation from a linear (trans) to a V‐shaped (cis) state. This increase in molecular distortion along with electrostatic repulsions of the positively charged bipyridine‐H\(^{+}\) units attenuate the aggregation tendency and induce a transformation from long fibers to shorter thinner fibers. Our findings may contribute to opening up new directions in molecular switches and stimuli‐responsive supramolecular materials.
Bei der Einelektronenreduktion eines durch eine cyclisches (Alkyl)(amino)carben (CAAC) stabilisierten Arylborylen-Carbonylkomplexes erfolgt die Bildung eines dimeren Borylketyl-Radikalanions, bedingt durch eine intramolekulare Arylmigration zum CO Kohlenstoffatom. Computergestützte Analyse liefert Hinweise auf eine radikalanionische [(CAAC)B(CO)Ar]\(^{.-}\) Zwischenstufe. Weiterführende Reduktion des entstandenen Komplexes liefert ein hoch nukleophiles (Boranyliden)methanolat.
Isolated 2‐phenylallyl radicals (2‐PA), generated by pyrolysis from a nitrite precursor, have been investigated by IR/UV ion dip spectroscopy using free electron laser radiation. 2‐PA is a resonance‐stabilized radical that is considered to be involved in the formation of polycyclic aromatic hydrocarbons (PAH) in combustion, but also in interstellar space. The radical is identified based on its gas‐phase IR spectrum. Furthermore, a number of bimolecular reaction products are identified, showing that the self‐reaction as well as reactions with unimolecular decomposition products of 2‐PA form several PAH efficiently. Possible mechanisms are discussed and the chemistry of 2‐PA is compared with the one of the related 2‐methylallyl and phenylpropargyl radicals.
The present work presents investigations on energy and charge transport properties in organic crystals. Chapter 4 treats exciton transport in anthracene, which is an example for weakly coupled π-systems. The electronic coupling parameter is evaluated by the monomer transition density approach. With these and the reorganization energy hopping rates are calculated in the framework of the Marcus theory. Together with the knowledge of the crystal structure, these allow us to calculate the experimental accessible exciton diffusion lengths, whose isotropic part fits nicely within the scattering of experimental values found in the literature. Furthermore, the anisotropy of the exciton diffusion lengths is reproduced qualitatively and quantitatively correct. This chapter also contains studies about electron and hole transport in both polymorphs (α and β) of perylene. Reorganization energies as well as diffusion coefficients for both crystal structures and types of charge transport were calculated. The best transport is hole transport in β-perylene, but it is strongly isotropic. The preferred transport direction is along the b-axis of the unit cell with couplings of greater than 100 meV. However, there is no transport along the c-axis. The diffusion constant in b-direction is bigger by two orders of magnitude than in c-direction (62.7•10-6 m2/s vs. 0.4•10-6 m2/s). Charge transport is calculated to be strongly anisotropic for holes as well as electrons in both modifications. To verify these results experimental electron mobilities have been compared to the simulations. Good agreement was found with errors of less than 27%. As it was shown above, the calculation and measurement of transport properties between weakly coupled systems is possible. However, it is difficult to exactly determine the quality of the electronic coupling. For this reason a collaboration about strongly interacting π-systems was started between us and the research group of Prof. Ingo Fischer. There, [2.2]paracyclophanes and its derivates were investigated to show how hydroxyl substitution influences absorption properties. Overall, a combination of SCS-MP2 and SCS-CC2 performs best to address the description of geometric and electronic structures for both ground and excited states of these model systems as well as their parent compounds benzene and phenol. Only [2.2]paracyclophane shows a double minimum potential regarding a twist and shift motion between the benzene/phenol subunits towards each other. All other systems are less flexible due to their substitution pattern. Almost all [2.2]paracyclophanes display minor changes in their geometric structure upon excitation to the S1 state: The inter-ring distance shortens, but qualitatively they keep their shift and twist characteristics, although the extent of these deformations diminishes. The exception is p-DHPC, which turns from a shifted ground state structure into a twisted excited state structure. Consequently, the intensity of the 0-0 transition cannot be observed experimentally due to small Franck-Condon factors and impurities of o-DHPC. In the present thesis, the structures and their changes due to excitation are explained by electrostatic potentials as well as antibonding (bonding) HOMO (LUMO) orbitals. Adiabatic excitation energies have been corrected by ZPEs and result in accuracies with errors smaller than 0.1 eV. Note that corrections on the B3LYP level worsen the results and one has to apply SCS-CC2 to achieve this accuracy. These calculations allow an interpretation of the experimental [1+1]REMPI spectra. Band progressions of the twist, shift and breathing of the [2.2]paracyclophane skeleton vibrations have been identified and show good agreement to the experiment. This work shows that the substitution pattern in [2.2]paracyclophanes can have a significant impact on spectroscopic properties. Because these properties are directly linked to the transport properties of these materials, the hereby gained insight can be used to design materials with customized transport properties. It was shown that the SCS-CC2 method is very appropriate to predict the interaction between the π-systems
In der vorliegenden Arbeit wurden zwei spektroskopische Methoden (Raman- und Circulardichroismus-Spektroskopie) und die Kernspinresonanz zur Untersuchung der Sekundärstruktur von synthetischen Polypeptiden eingesetzt. Dabei wurden die Struktur-Funktions-Beziehungen der dritten extrazellulären Schleife des Gonadotropin-freisetzenden Rezeptors (GnRH-R) untersucht. Die spektroskopischen Ergebnisse belegten, dass die zuvor getroffene Aussage über eine vorhandene helikale Struktur revidiert werden musste. Die Strukturanalysen mit Hilfe der CD-, Raman- und 2D NMR-Experimente an zwei Serien von Polypeptiden lieferten Aussagen über die Sekundärstruktur. Insbesondere die Raman-Untersuchungen in Verbindung mit einer statistischen Datenanalyse lieferten detaillierte Information über subtile Konformationsänderungen, die einerseits durch die Addition und andererseits durch die Substitution einzelner Aminosäuren in den synthetischen Polypeptiden ausgelöst wurden. Anhand der ausgewählten Raman-Linien konnte nachgewiesen werden, dass sowohl die Änderungen der Polypeptidkettenlänge als auch die Änderung der Polypeptidsequenzen mit den beobachteten Intensitäten der Raman-Linien korreliert sind.
Infrared (IR) and Raman spectroscopy are among the most widely used techniques in the physical and natural sciences today. Vibrational spectroscopy, including IR and Raman spectroscopy, has both a long and interesting history and an illustrious record of contributions to science. Spectroscopy in the pharmaceutical industry is dominated by techniques such as nuclear magnetic resonance (NMR) and mass spectrometry (MS) for the elucidation of chemical structures. Despite this, the versatility of infrared spectroscopy ensures it still remains a key technique in quality control laboratories, and in applications where solid form characterization or minimal sample preparation is a necessity. Raman spectroscopy has many uses in the pharmaceutical and chemical industry, but its strengths is in solid form analysis. It is regularly used to identify compounds, and results are used in the release of pharmaceutical and chemical products. This work consists of 8 chapters, which cover the vibrational spectroscopy beginning with the theory and instrumentation, continuing with the experimental setup and probes description, and completing with results and discussions of the experiments. The first chapter of this work introduces Raman spectroscopy as a dominant technique used in pharmaceutical and chemical industry. The theoretical background regarding vibrational spectroscopy (IR and Raman) is accounted for in the second chapter of this work, while the samples presentation, the experimental procedures, and the description of the apparatus together with the computational details are briefly specified in the third chapter. The fourth chapter investigates the concentration dependent wavenumber shifts and linewidth changes of tetrahydrofuran in a binary system. Many of the applications in food science rely heavily on Raman spectroscopy, often preceding the biomedical applications. The characterization and identification of food additives using Raman, surface-enhanced Raman spectroscopy, and theoretical calculations is in detail depicted in the fifth chapter, whereas in the sixth and seventh chapters the monitoring of several medicines and various lanthanide complexes with anticancer properties, respectively, employing IR and Raman techniques are treated. These last two chapters address applications of vibrational spectroscopy to pharmaceutical products, and include the use of vibrational spectroscopy in combinatorial chemistry and density functional theory, a modality increasingly used by the pharmaceutical industry for the discovery if new pharmacologically active substances.
In the current work, several well-known pharmaceuticals (1,4-dihydrazinophthalazine sulfate, caffeine, and papaverine hydrochloride) and new organometallic compounds (nickel(II) cupferronato complexes NiL2An, L = PhN2O2-, n = 1, A = o-phenanthroline (1), o,o’-bipyridine (2) and n = 2, A = H2O (3), o-NH2Py (4), o-C6H4(NH2)2 (5); silylene-bridged dinuclear iron complexes [Cp(OC)2Fe]2SiX2 (X = H (6), F (7), Cl (8), Br (9), I (10)); 3-silaoxetane 3,3-dimethyl-2,2,4,4-tetraphenyl-1-oxa-3-silacyclobutane (11) and 3-silathietane 3,3-dimethyl-2,2,4,4-tetraphenyl-1-sila-3-thiacyclobutane (12) compounds), which have successfully been characterized by using vibrational spectroscopy in conjunction with accurate density functional theory (DFT) calculations, are presented. The DFT computed molecular geometries of the species of interest reproduced the crystal structure data very well and in conjunction with IR and Raman measurements helped us to clarify the structures of the compounds, for which no experimental data were available; and this, especially for the new organometallic compounds, where the X-Ray analysis was limited by the non-availability of single crystals (3, 5, 10). Furthermore, a natural population analysis (NPA) and natural bond orbital (NBO) calculations together with a detailed analysis of the IR and Raman experimental as well as calculated spectra of the new organometallic compounds, allowed us to study some special bonding situations (1-12) or to monitor the structural changes observed with the change in temperature during the Raman experiments (11, 12). By combining these two methods (DFT and vibrational spectroscopy), the auspicious results obtained on the organometallic compounds 6-12 and overall in literature, made us confident of the power of theoretical calculations in aiding the interpretation of rich SERS spectra by solving some interesting issues. Consequently, the Raman and SERS spectra of well-known pharmaceuticals (1,4-dihydrazinophthalazine sulfate, caffeine, and papaverine hydrochloride) or new potentially biological active organometallic complexes (1-5), that were synthetized by our coworkers, were discussed with the assistance of the accurate results obtained from DFT calculations (structural parameters, harmonic vibrational wavenumbers, Raman scattering activities), and many previous incomplete assignments have been analyzed and improved. This allowed us to establish the vibrational behavior of these biological compounds near a biological artificial model at different pH values or concentrations (Ag substrate), taking into account that information about the species present under particular conditions could be of great importance for the interpretation of biochemical processes. The total electron density of molecules and the partial charges situated on selected atoms, which were determined theoretically by NPA, allowed us to establish the probability of different atoms acting as an adsorptive site for the metal surface. Moreover, a closer examination of the calculated orbitals of molecules brought further arguments on the presence or absence of the photoproducts at the Ag surface during the irradiation (1,4-dihydrazinophthalazine sulfate). Overall, the results provide a benchmark illustration of the virtues of DFT in aiding the interpretation of rich vibrational spectra attainable for larger polyatomic adsorbates by using SERS, as well as in furnishing detailed insight into the relation between the vibrational properties and the nature of the Ag substrate-adsorbate bonding. Therefore, we strongly believe that theoretical calculations will become a matter of rapidly growing scientific and practical interest in SERS.
The SARS virus is the etiological agent of the severe acute respiratory syndrome, a deadly disease that caused more than 700 causalities in 2003. One of its viral proteins, the SARS coronavirus main protease, is considered as a potential drug target and represents an important model system for other coronaviruses. Despite extensive knowledge about this enzyme, it still lacks an effective anti-viral drug. Furthermore, it possesses some unusual features related to its active-site region. This work gives atomistic insights into the SARS coronavirus main protease and tries to reveal mechanistic aspects that control catalysis and inhibition. Thereby, it applies state-of-the-art computational methods to develop models for this enzyme that are capable to reproduce and interpreting the experimental observations. The theoretical investigations are elaborated over four main fields that assess the accuracy of the used methods, and employ them to understand the function of the active-site region, the inhibition mechanism, and the ligand binding. The testing of different quantum chemical methods reveals that their performance depends partly on the employed model. This can be a gas phase description, a continuum solvent model, or a hybrid QM/MM approach. The latter represents the preferred method for the atomistic modeling of biochemical reactions. A benchmarking uncovers some serious problems for semi-empirical methods when applied in proton transfer reactions. To understand substrate cleavage and inhibition of SARS coronavirus main protease, proton transfer reactions between the Cys/His catalytic dyad are calculated. Results show that the switching between neutral and zwitterionic state plays a central role for both mechanisms. It is demonstrated that this electrostatic trigger is remarkably influenced by substrate binding. Whereas the occupation of the active-site by the substrate leads to a fostered zwitterion formation, the inhibitor binding does not mimic this effect for the employed example. The underlying reason is related to the coverage of the active-site by the ligand, which gives new implications for rational improvements of inhibitors. More detailed insights into reversible and irreversible inhibition are derived from in silico screenings for the class of Michael acceptors that follow a conjugated addition reaction. From the comparison of several substitution patterns it becomes obvious that different inhibitor warheads follow different mechanisms. Nevertheless, the initial formation of a zwitterionic catalytic dyad is found as a common precondition for all inhibition reactions. Finally, non-covalent inhibitor binding is investigated for the case of SARS coranavirus main protease in complex with the inhibitor TS174. A novel workflow is developed that includes an interplay between theory and experiment in terms of molecular dynamic simulation, tabu search, and X-ray structure refinement. The results show that inhibitor binding is possible for multiple poses and stereoisomers of TS174.
In the present contribution, we describe the synthesis of highly dispersed silver nanorods (NRs) of different aspect ratios using a chemical route. The shape and size of the synthesized NRs were characterized by Transmission Electron Microscopy (TEM) and UV-visible spectroscopy. Longitudinal and transverse absorptions bands confirm the rod type structure. The experimentally recorded UV-visible spectra of NRs solutions were fitted by using an expression of the extinction coefficient for rod like nano structures under the dipole approximation. Simulated and experimentally observed UV-visible spectra were compared to determine the aspect ratios (R) of NRs. The average values of R for NR1, NR2 and NR3 solutions are estimated to be 3.0 ± 0.1, 1.8 ± 0.1 and 1.2 ± 0.1, respectively. These values are in good agreement with those obtained by TEM micrographs. The silver NRs of known aspect ratios are used to study antimicrobial activities against B. subtilis (gram positive) and E. coli (gram negative) microbes. We observed that the NRs of intermediate aspect ratio (R = 1.8) have greater antimicrobial effect against both, B. subtilis (gram positive) and E. coli (gram negative). The NRs of aspect ratio, R = 3.0 has better antimicrobial activities against gram positive than on the gram negative.
Covalent peptidomimetic protease inhibitors have gained a lot of attention in drug development in recent years. They are designed to covalently bind the catalytically active amino acids through electrophilic groups called warheads. Covalent inhibition has an advantage in terms of pharmacodynamic properties but can also bear toxicity risks due to non-selective off-target protein binding. Therefore, the right combination of a reactive warhead with a well-suited peptidomimetic sequence is of great importance. Herein, the selectivities of well-known warheads combined with peptidomimetic sequences suited for five different proteases were investigated, highlighting the impact of both structure parts (warhead and peptidomimetic sequence) for affinity and selectivity. Molecular docking gave insights into the predicted binding modes of the inhibitors inside the binding pockets of the different enzymes. Moreover, the warheads were investigated by NMR and LC-MS reactivity assays against serine/threonine and cysteine nucleophile models, as well as by quantum mechanics simulations.
Tetraiododiborane(4) (B\(_2\)I\(_4\)) is a Polymer based on sp\(^3\) Boron in the Solid State
(2020)
Herein we present the first solid‐state structures of tetraiododiborane(4) (B\(_2\)I\(_4\)), which was long believed to exist in all phases as discrete molecules with planar, tricoordinate boron atoms, like the lighter tetrahalodiboranes(4) B\(_2\)F\(_4\), B\(_2\)Cl\(_4\), and B\(_2\)Br\(_4\). Single‐crystal X‐ray diffraction, solid‐state NMR, and IR measurements indicate that B\(_2\)I\(_4\) in fact exists as two different polymeric forms in the solid state, both of which feature boron atoms in tetrahedral environments. DFT calculations are used to simulate the IR spectra of the solution and solid‐state structures, and these are compared with the experimental spectra.
The present studies which have been performed in the work-group C-2 (Prof. W. Kiefer) within the program of the Sonderforschungsbereichs 347, deal with the FT-Raman and –IR spectroscopy on new organometallic complexes, synthesized in the work-groups B-2 (Prof. W. Malisch), B-3 (Prof. W. A. Schenk), D-1 (Prof. H. Werner) and D-4 (Prof. D. Stalke). The FT-Raman spectra recorded at 1064 nm led to very useful and interesting information. Furthermore, the DFT calculations which are known to offer promise of obtaining accurate vibrational wavenumbers, were successfully used for the assignment of the vibrational spectra. For the first time it has been possible to ascribe exactly the n(RhC) stretching mode in the vinylidene rhodium(I) complex trans-[RhF(=C=CH2)(PiPr3)2] by using isotopic substitution, in conjunction with theoretical calculations. This is also true for the complexes trans-[RhF(CO)(PiPr3)2], trans-[RhF(C2H4)(PiPr3)2], trans-[RhX(=C=CHPh)(PiPr3)2] (X = F, Cl, Br, I, Me, PhCºC) and trans-[RhX(CN-2,6-xylyl)(PiPr3)2] (X = F, Cl, Br, I, CºCPh). In addition, the comparison between the n(RhC) wavenumbers of the complexes trans-[RhF(=13C=13CH2)(PiPr3)2] and trans-[RhF(CO)(PiPr3)2], containing the isoelectronic ligands 13C=13CH2 and CO, which have the same reduced mass, indicated that the Rh-C bond is stronger in the carbonyl than in the vinylidene complex. Besides, the n(RhF) stretching mode, which has been observed at higher wavenumbers in the FT-Raman and -IR spectra of trans-[RhF(CO)(PiPr3)2], showed that the carbonyl ligand is a better p-acceptor and a less effective s-donor than the vinylidene one. Moreover, the comparison of the n(CºC) and n(Rh-C) modes from the FT-Raman spectrum of the complexes trans-[Rh(CºCPh)(L)(PiPr3)2] (L = C=CHPh, CO, CN-2,6-xylyl) point out that the p-acceptor ability of the ligand trans to CºCPh should rise in the order C=CH2 < CO < CN-2,6-xylyl £ C=CHPh. The investigated sensitivity of the n(RhC), n(CC), n(CO) and n(CN) vibrational modes to the electronic modifications occuring in the vinylidene, carbonyl, ethylene and isonitrile complexes, should allow in the future the examination of the p-acceptor or p-donor properties of further ligands. Likewise, we were able to characterize the influence of various X ligands on the RhC bond by using the n(RhC) stretching mode as a probe for the weakening of this. The calculated wavenumbers of the n(RhC) for the vinylidene complexes trans-[RhX(=C=CHR)(PiPr3)2], where R = H or Ph, suggested that the strength of the Rh=C bond increases along the sequence X = CºCPh < CH3 < I < Br < Cl < F. For the series of carbonyl compounds trans-[RhX(CO)(PiPr3)2], where X = F, Cl, Br and I, analogous results have been obtained and confirmed from the model compounds trans-[RhX(CO)(PMe3)2]. Since, the calculated vibrational modes for the ethylene complex trans-[RhF(C2H4)(PiPr3)2] were in good agreement with the experimental results and supported the description of this complex as a metallacyclopropane, we were interested in getting more information upon this class of compounds. In this context, we have recorded the FT-Raman and -IR spectra of the thioaldehyde complexes mer-[W(CO)3(dmpe)(h2-S=CH2)] and mer-[W(CO)3(dmpe)(h2-S=CD2)] which have been synthezised by B-3. The positions of the different WL vibrational modes anticipated by the DFT calculations, were consistent with the experimental results. Indeed, the analysis of the band shifts in the FT-Raman and –IR spectra of the isotopomer mer-[W(CO)3(dmpe)(h2-S=CD2)] confirmed our assignment. The different stereoisomers of complex mer-[W(CO)3(dmpe)(h2-S=CH2)] were investigated too, since RMN and IR-data have shown that complex mer-[W(CO)3(dmpe)(h2-S=CH2)] lead in solution to an equilibrium. Since the information on the vibrational spectra of the molybdenum and tungsten complexes Cp(CO)2M-PR2-X (M = Mo, W; R = Me, tBu, Ph; X = S, Se) is very scarce, we extended our research work to this class of compounds. We have tried to elucidate the bonding properties in these chalcogenoheterocycle complexes by taking advantage of the mass effect on the different metal atoms (W vs. Mo). Thus, the observed band shifts allowed to assign most of the ML fundamental modes of these complexes. This project and the following one were a cooperation within the work-group B-2. The Raman and IR spectra of the matrix isolated photoproducts expected by the UV irradiation of the iron silyl complex Cp(CO)2FeSiH2CH3 have been already reported by Claudia Fickert and Volker Nagel in their PhD-thesis. Since no exact assignment was feasible for these spectra, we were interested in the study of the reaction products created by irradiation of the carbonyl iron silyl complex Cp(CO)2FeCH2SiH3. Although the calculated characteristic vibrational modes of the metal ligand unit for the various photoproducts are significantly different in constitution, they are very similar in wavenumbers, which did not simplify their identification. However, the theoretical results have been found to be consistent with the earlier experimental results. Finally, the last part of this thesis has been devoted to the (2-Py)2E- anions which exhibit a high selectivity toward metal-coordination. All di(2-pyridyl) amides and -phosphides which were synthesized by D-4, coordinate the R2Al+ fragment via both ring nitrogen atoms. This already suggests that the charge density in the anions is coupled into the rings and accumulated at the ring nitrogen atoms, but the Lewis basicity of the central nitrogen atom in Et2Al(2-Py)2N is still high enough to coordinate a second equivalent AlEt3 to form the Lewis acid base adduct Et2Al(2-Py)2NAlEt3. Due to the higher electronegativity of the central nitrogen atom in Me2Al(2-Py)2N, Et2Al(2-Py)2N and Et2Al(2-Py)2NAlEt3, compared to the bridging two coordinated phosphorus atom in Me2Al(2-Py)2P and Et2Al(2-Py)2P, the di(2-pyridyl)amide is the hardest Lewis base. In the phosphides merely all charge density couples into the rings leaving the central phosphorus atom only attractive for soft metals. These results were confirmed by using DFT and MP2 calculations. Moreover, a similar behaviour has been observed and described for the benzothiazolyl complex [Me2Al{Py(Bth)P}], where complementary investigations are to be continued. The DFT calculations carried out on the model compounds analysed in these studies supply very accurate wavenumbers and molecular geometries, these being in excellent agreement with the experimental results obtained from the corresponding isolated complexes.
Ziel dieser Arbeit war es, die Möglichkeiten zur Verwendung des Auges bzw. der Augenvorderkammer als spektroskopische Zelle für nicht-invasive In-vivo-Messungen zu untersuchen. Dabei stand vor allem die Geräte-technische Umsetzung und die Entwicklung geeigneter Auswertestrategien im Vordergrund. In dieser Arbeit konnte gezeigt werden, dass die spektroskopische Untersuchung von Kammerwasser-Substanzen möglich ist. Durch den Einsatz der UV/VIS-Spektroskopie konnte Fluorescein in vivo bestimmt werden. Die Anwendung der NIR-Spektroskopie eignet sich vor allem zur Bestimmung von Glucose im Kammerwasser. Die Güte der Glucose-Bestimmung ist von verschiedenen Faktoren abhängig, wie z. B. dem verwendeten Gerät, den Parameter der Auswertung und der Temperatur. Für weitergehende Studien sollten daher die in dieser Arbeit aufgedeckten Probleme und Strategien beachtet werden.
The first is via direct dissociation and the second likely involves a barrier slowing down dissociation.
Chlorine-containing hydrocarbons pose a great risk for the environment and especially for the atmosphere. In this thesis I present the photodissociation dynamics of multiple chlorine-containing molecules. The method of velocity map imaging was utilized for gaining information on the kinetic energy distribution of the fragments generated in the photodissociation reactions.
First, the photodissociation of benzoyl chloride after excitation to the S1, S2 and the S3 state between 279 nm and 237 nm was studied. This stable molecule was an ideal candidate for demonstrating a new ionization scheme for chlorine atoms. It was shown that benzoyl chloride dissociates statistically from the ground state.
Afterwards, the results from experiments on the radicals trichloromethyl and dichlorocarbene are presented in the range of 230 to 250 nm. These radicals remain after the dissociation of carbon tetrachloride and have not been studied in detail because of their instability. Trichlormethyl dissociates via two paths: The loss of a chlorine atom to dichlorocarbene and by decaying to CCl and a chlorine molecule. The dissociation to dichlorocarbene involves a barrier. If the photon exciting the molecule has enough energy to surpass the barrier, which is the case starting at around 235 nm, trichlormethyl dissociates rapidly resulting in an anisotropic VMI. However, if the the excitation energy is lower, the dissociation takes longer than a rotational period and the anisotropy is lost.The path to CCl is a statistical dissociation.
Dichlorocarbene dissociates to CCl and Cl via to separate channels. The first is via direct dissociation and the second likely involves a barrier slowing down dissociation.
In this work, the laser control of molecules was investigated theoretically. In doing so, emphasis was layed on entering vectorial properties and in particular the orientation in the laboratory frame. Therefore, the rotational degree of freedom had to be included in the quantum mechanical description. The coupled vibrational and rotational dynamics was examined, which is usually not done in coherent control theory. Local control theory was applied, where the field is determined from the dynamics of a system, which reacts with an instantaneous response to the perturbation and, in turn, determines the field again. Thus, the field is entangled with the quantum mechanical motion and the presented examples document, that this leads to an intuitive interpretation of the fields in terms of the underlying molecular dynamics. The limiting case of a classical treatment was shown to give similar results and hence, eases to understand the complicated structure of the control fields. In a different approach, the phase- and amplitude shaping of laser fields was systematically studied in the context of controlling population transfer in molecules.
Femtosekunden-zeitaufgelöste transiente Absorptionsspektroskopie einer neutralen organischen gemischtvalenten Verbindung In einem Femtosekunden-zeitaufgelösten Anrege-Abfrage-Experiment wurde die Dynamik des Elektronentransfers einer neutralen organischen gemischtvalenten Verbindung untersucht. Neben der Abhängigkeit des Rückelektronentransfers von der Solvenspolarität wurde auch die Rotationsdiffusion in n-Hexan, Toluol, Dibutylether, tert-Butylmethylether und Benzonitril studiert. Die transiente Dynamik lässt sich mit einer Lebensdauer beschreiben, verursacht durch einen Rückelektronentransfer. Während dieser in unpolaren Lösemitteln relativ langsam verläuft, beobachtet man deutlich schnellere ET-Raten mit steigender Polarität des Lösemittels. Die Lebensdauer variiert von 1.2 ps für Benzonitril bis 260 ps für n-Hexan. Rotationsdiffusion konnte nicht beobachtet werden. Die gemessenen Raten wurden mit theoretischen Raten verglichen. Für unpolare Lösemittel konnte eine gute Übereinstimmung gefunden werden. In polaren Lösemitteln bewirkt eine Korrektur, die die Solvensrelaxationszeit berücksichtigt, eine sehr gute Übereinstimmung von berechneten und gemessenen Rückelektronentransferraten. Zeit- und frequenzaufgelöste Photoionisation des C 2A2-Zustandes des Benzylradikals Die Lebensdauer des C 2A2-Zustandes des Benzylradikals wurde in Abhängigkeit der Überschussenergie bestimmt. Die zeitabhängigen Ionensignale konnten dabei mit einer biexponentiellen Dynamik beschrieben werden. Bei einer Anregung am Ursprung (305nm) betragen die Lebensdauern τ1= 400 fs und τ2 = 4.5 ps. Die kürzere Lebensdauer τ1 beschreibt die interne Konversion vom C-Zustand zu den stark koppelnden A/B-Zuständen, die längere Lebensdauer τ2 die interne Konversion von den A/B-Zuständen in den elektronischen Grundzustand. Mit steigender Anregungsenergie beobachtet man eine stete Abnahme beider Lebensdauern. Bei einer Anregung mit einem Puls der Wellenlänge von 301 nm beobachtet man deutlich kürzere Lebensdauern mit τ1 = 350 fs und τ2 = 2.8 ps. Erfolgt die Anregung mit einem Puls der Wellenlänge von 298 nm, betragen die Zeitkonstanten τ1 = 180 fs und τ2 = 2.1 ps. Desweiteren konnte ein zeitabhängiges Ionensignal für eine Spezies mit der Zusammensetzung C7H5 beobachtet werden. Der Träger des Signals ist das Fulvenallenylradikal.
We introduce a new approach to transient spectroscopy, fluorescence‐detected pump–probe (F‐PP) spectroscopy, that overcomes several limitations of traditional PP. F‐PP suppresses excited‐state absorption, provides background‐free detection, removes artifacts resulting from pump–pulse scattering, from non‐resonant solvent response, or from coherent pulse overlap, and allows unique extraction of excited‐state dynamics under certain conditions. Despite incoherent detection, time resolution of F‐PP is given by the duration of the laser pulses, independent of the fluorescence lifetime. We describe the working principle of F‐PP and provide its theoretical description. Then we illustrate specific features of F‐PP by direct comparison with PP, theoretically and experimentally. For this purpose, we investigate, with both techniques, a molecular squaraine heterodimer, core–shell CdSe/ZnS quantum dots, and fluorescent protein mCherry. F‐PP is broadly applicable to chemical systems in various environments and in different spectral regimes.
Nonlinear frequency conversion of low-energy fs laser pulses was investigated in solid-state media. Raman conversion in the white-light-free regime of impulsive stimulated Raman scattering was achieved by pumping KGW crystal with Bessel beam. Efficient supercontinuum generation was demonstrated for sub-microjule pulses focused into microstructure fiber. Application of four-wave mixing techniques to monitoring of the excited-state dynamics in polyatomic molecules was demonstrated. Time constants of the processes related to vibrational energy redistribution upon the initial photoexcitation of stilbene-3 were determined by means of pump-CARS technique, where CARS process served as an effective mode-selective filter. Spectral as well as temporal properties of electronic relaxation pathway in azulene derivatives were explored by using transient population gratings and pump-probe transient absorption techniques.
The goal of this thesis was the development and application of higher-order spectroscopic techniques. In contrast to ordinary pump–probe (PP) and two-dimensional (2D) spectroscopy, higher-order coherently detected spectroscopic methods measure a polarization that has an order of nonlinearity higher than three. The key idea of the techniques in this thesis is to isolate the higher-order signals from the lower-order signals either by their excitation frequency or by their excitation intensity dependence. Due to the increased number of interactions in higher-order spectroscopy, highly excited states can be probed. For excitonic systems such as aggregates and polymers, the fifth-order signal allows one to directly measure exciton–exciton annihilation (EEA). In polymers and aggregates, the exciton transport is not connected to a change of the absorption and can therefore not be investigated with conventional third-order techniques. In contrast, EEA can be used as a probe to study exciton diffusion in these isonergetic systems. As a part of this thesis, anisotropy in fifth-order 2D spectroscopy was investigated and was used to study geometric properties in polymers.
In 2D spectroscopy, the multi-quantum signals are separated from each other by their spectral position along the excitation axis. This concept can be extended systematically to higher signals. Another approach to isolate multi-quantum signals in PP spectroscopy utilizes the excitation intensity. The PP signal is measured at specific excitation intensities and linear combinations of these measurements result in different signal contributions. However, these signals do not correspond to clean nonlinear signals because the higher-order signals contaminate the lower-order multi-quantum signals. In this thesis, a correction protocol was derived that uses the isolated multiquantum signals, both from 2D spectroscopy and from PP spectroscopy, to remove the contamination of higher-order signals resulting in clean nonlinear signals. Using the correction on the third-order signal allows one to obtain annihilation-free signals at high excitation intensities, i.e., with high signal-to-noise ratio. Isolation and correction in PP and 2D spectroscopy were directly compared by measuring the clean third-order signals of squaraine oligomers at high excitation intensities. Furthermore, higher-order PP spectroscopy was used to isolate up to the 13th nonlinear order of squaraine polymers.
The demonstrated spectroscopic techniques represent general procedures to isolate clean signals in terms of perturbation theory. The technique of higher-order PP spectroscopy needs only small modifications of ordinary PP setups which opens the field of higher-order spectroscopy to the broad scientific community. The technique to obtain clean nonlinear signals allows one to systematically increase the number of interacting (quasi)particles in a system and to characterize their interaction energies and dynamics.
This work focuses on theoretical approaches for predicting the valence and core excited states of aggregate systems. For the valence excitations, TD-HF and TD-DFT with different functionals have been tested at the Perylene bisimide (PBI) system. A simple character analysis method based on the calculated transition dipole moments is proposed. However, this method does not work for excited states without any transition dipole moment. Thus, we proposed a more general and more valid method based on a calculated CIS type wavefunction for the character analysis. Furthermore, a model Hamiltonian method is derived from a localized picture. The energies of the diabatic states and the corresponding coupling parameters were also determined on the basis of ab initio calculations. For the core excitation, three different methods were validated for C 1s-excited and ionized states if several small molecules. Also we tested the basis sets dependence of these core excited states. Based on those results, we chose the frozen core approximation method to evaluate the core excited states of NTCDA molecules. In order to explain the findings in the experiments, we developed an algorithm to evaluate the exciton coupling parameter where non-orthogonal MOs are used.
A series of combustion relevant species like radicals, carbenes and polycyclic aromatic hydrocarbons were characterized in the gas phase by vacuum UV synchrotron radiation and their ionization energies (IE) and further spectroscopic details of the respective cations were retrieved from threshold photoelectron spectra. The reactive intermediates were generated by flash vacuum pyrolysis from stable precursor molecules. Furthermore three polycyclic aromatic hydrocarbons were investigated by threshold photoelectron spectroscopy, too. The experiment was performed at the VUV beamline of the Swiss Light Source in Villigen/Switzerland and the iPEPICO (imaging photoelectron photoion coincidence) setup was applied to correlate ions and electrons from the same ionization event. From the threshold photoelectron spectra and from quantum chemical computations the vibrational structure of the molecule cations and the geometry changes upon ionization were assigned. The ionization energies of the two C4H5 isomers 2-butyn-1-yl and 1-butyn-3-yl were assigned to 7.94±0.02 eV and 7.97±0.02 eV, respectively. The isomerization between the two isomers was computed to have a barrier of 2.20 eV, so a rearrangement between the two radicals cannot be excluded. From the threshold photoelectron spectra of the two constitutional C4H7 isomers 1-methylallyl and 2-methylallyl the ionization energies were assigned to 7.48±0.02 eV and to 7.59±0.02 eV for 1-E-methylallyl and 1-Z-methylallyl, as well as to 7.88±0.01 eV for 2-methylallyl. The two radicals 9-fluorenyl, C13H9, and benzhydryl, C13H11, were observed to ionize at 7.01±0.02 eV and 6.7 eV. The threshold photoelectron spectrum of benzhydryl also incorporated the signal of the diphenylmethyl carbene, C13H10, which has an IE at 6.8 eV. In addition, the head-to-head dimers of 9-fluorenyl and benzhydryl were observed as products in the pyrolysis. C26H18 has an IE at 7.69±0.04 eV and C26H22 has an IE at 8.13±0.04 eV. The three polycyclic aromatic hydrocarbon DHP (C14H16) 1-PEN (C18H22) and THCT (C22H16) were investigated in an effusive beam. The ionization energies were determined to IE(DHP)= 7.38±0.02 eV, IE(1-PEN)=7.58±0.05 eV and IE(THCT)=6.40±0.02 eV. Furthermore the thermal decomposition and the dissociative photoionization of diazomeldrum’s acid was investigated. The pyrolysis products yielded beside several other products the two not yet (by photoelectron spectroscopy) characterized molecules E-formylketene, C3O2H2 and 2-diazoethenone, N2C2O. The dissociative photoionization showed the Wolff rearrangement to occur at higher internal energies.
Im ersten Teil wurde die Dynamik des ersten angeregten Zustandes von drei Truxenonen untersucht. Nach Anregung im sichtbaren Bereich findet ein Elektrontransfer zwischen den Triarylamin-Donor und dem Truxenon-Akzeptor statt. Um die Abhängigkeit der Rate für den Rücktransfer von der elektronischen Kopplung zu untersuchen, wurde diese zum einen über den Abstand zwischen Donor und Akzeptor und zum anderen über die Position der Verknüpfung eingestellt. In einer ersten Studie wurde Truxenon 1, bei dem der direkt über das Stickstoff-Atom an den Akzeptor gekuppelt ist, mit dem System 2 verglichen, bei den die Einheiten über einen Phenyl-Spacer verbunden sind. Der Rücktransfer sollte dabei für das System 1 schneller sein, da ein kurzer Abstand mit einer starken elektronischen Kopplung einhergeht und damit auch mit einem schnellen Elektronentransfer. Allerdings wird die große Rate für das System mit dem größeren Abstand beobachtet (2). Dieses Ergebnis kann mit der Geometrie der Moleküle und der größeren sterischen Hinderung in 1 erklärt werden, aus der eine geringere elektronische Kopplung resultiert. In einem weiteren Experiment wurde die Stärke der elektronischen Kopplung in Abhängigkeit von der Position der Verknüpfung in Bezug auf den Phenyl-Spacer untersucht. Zu diesem Zweck wurden die Systeme 2 und 3 miteinander verglichen. Während in 2 die Einheiten in para-Position verknüpft sind, sind Donor und Akzeptor in 3 in meta-Position an den Phenyl-Spacer gekuppelt. Letzteres System zeichnet sich dabei durch eine geringere Resonanzstabilisierung aus. Dies hat eine geringere elektronische Kopplung zur Folge, was sich auch in den UV/Vis-Spektren zeigt. Die langwelligste Absorption ist hier bei höheren Energien zu beobachten. Zudem deuten die transienten Spektren an, dass in erster Linie nicht der ladungsgetrennte Zustand abgeregt wird sondern vielmehr die Truxenon-Einheit selbst. Im zweiten Teil wurden die Resonanz-Raman-Spektren vier verschiedener Borole aufgenommen. Dabei wurden zwei signifikanten Moden beobachtet, die beim pi –pi∗ -Übergang in ihrer Intensität verstärkt werden. Eine Bande bei 1598 cm-1 wird der symmetrischen Ringatmung zugeordnet, die aus einer Expansion des Borol-Rings resultiert. Eine zweite Schwingung bei 1298 cm-1 resultiert aus einer B-R Streckschwingung. Für System 5 wird diese Schwingung mit einer hohen Intensität beobachtet, während die Bande bei den Systemen 6-8, die mit einem Aryl-Rest substituiert sind, mit sehr geringer Intensität auftritt und deshalb lediglich mit einem hochauflösendem Setup detektiert werden kann. Aufgrund der schwachen Resonanzverstärkung kann von einer schwachen Wechselwirkung zwischen dem Bor und dem Aryl-Rest ausgegangen werden. In Borol 5, in dem eine Ferrocen-Einheit an das Bor gebunden ist, ist die Situation eine andere: nach Anregung des pi-pi*-Übergangs wird die Population im BC_4-Ring verschoben. Dadurch kann vom Eisen keine Elektronendichte mehr in das p_z-Orbital des Bors verschoben werden, die Fe-B-Wechselwirkung wird geschwächt und der Fe-B-Abstand wird vergrößert. Zusammenfassend konnte gezeigt werden, dass die Eigenschaften des Substituenten großen Einfluss auf die elektronische Struktur eines dreifach-substituierten Bor-Atoms hat, das in einer p_z-pi-Konjugation beteiligt ist.
Light-induced excitation of matter proceeds within femtoseconds, resulting in excited states. Originating from these states chemical reaction mechanisms, like isomerization or bond formation, set in. Photophysical mechanisms like energy distribution and excitonic delocalization also occur. Thus, the reaction scheme has to be disentangled by assessing the importance of each process. Spectroscopic methods based on fs laser pulses have emerged as a versatile tool to study these reactions. Within this thesis time-resolved experiments with fs laser pulses on various molecular systems were performed. Novel photosystems, with possible applications ranging from ultrathin molecular wires to molecular switches, were extensively characterized. To resolve the complex kinetics of the investigated systems, time-resolved techniques had to be newly developed. By combining a visible excitation pulse pair with an additional pulse and a continuum probe electronic triggered-exchange two-dimensional spectroscopy (TE2D) was demonstrated for the first time. This goal was accomplished by combining a three-color transient-absorption setup with a pulse shaper. Hence, 2D spectroscopy with a continuum probe was also implemented. Using these methods two different molecular systems in solution were characterized in a comprehensive manner. (ZnTPP)2, a directly beta,beta’-linked Zn-metallated bisporphyrin, and a spiropyran-merocyanine photosystem, 6,8-dinitro BIPS, were characterized. (ZnTPP)2 is a homodimer, featuring strong excitonic effects. These manifest themselves in a twofold splitting of the Soret band (S2). 6,8-Dinitro BIPS exists in one of two possible conformations. The ring closed spiropyran absorbs only in the UV, while the ring open merocyanine also absorbs in the visible. For both molecular systems photodynamics upon illumination were monitored using transient-absorption. However, the obtained results were ambiguous, necessitating more complex methods. In the case of (ZnTPP)2 first the monomeric building block was characterized. There, population transfer from the S2 state into S1 within 2 ps was identified. Afterwards, intersystem crossing proceeds within 2 ns. For (ZnTPP)2 similar pathways were found, albeit the relaxation is faster. The intersystem crossing with 1.5 ns was not only indirectly deduced but directly measured by probing in the NIR spectral range. The excitonic influence of was investigated by coherent 2D spectroscopy in the Soret band. Population transfer within S2 was directly visualized on a time-scale of 100 fs. Calculation of the 2D spectra of a simple homodimer confirmed the results. After this analysis of the distinct excitonic character, this molecule may serve as a building block for larger porphyrin arrays with applications ranging from asymmetric catalysis over biomimicry of electron-transfer to organic optical devices. The second photosystem was the molecular switch 6,8-dinitro BIPS, existing in two conformations. Merocyanine is the more stable form in thermal equilibrium. Transient-absorption measurements uncovered that the sample consisted of a mixture of two merocyanine isomers, referred to as TTC and TTT. However, both isomers are capable of ring-closure forming spiropyran. The remaining excited molecules return to the ground state radiatively. Conducting 2D measurements utilizing a continuum probe the differing photochemistry of both isomers was examined in a single measurement. No isomerization between these conformations was detected. Therefore, 6,8-dinitro BIPS performs a concerted switching without long-living intermediates. This was confirmed by a pump-repump-probe scan. 6,8-DinitroBIPS can be closed by visible and opened by UV pulses using subsequent pulses and vice versa. These mechanisms via singlet pathways satisfy an important criterion for a unimolecular switching device. A second pump-repump-probe experiment showed that the sample is ionized, resulting in a merocyanine radical cation, when the first excited state is resonantly excited. Furthermore, by implementing TE2Dspectroscopy, it was elucidated that only TTC was ionized. Taking all this into account new techniques were developed and complex molecular systems were characterized within this thesis. Deeper insight into the photodynamics of (ZnTPP)2and 6,8-dinitro BIPS was gained by adapting transient absorption for the NIR spectral range, constructing a 2D setup in pump-probe geometry, and combining it with multipulse excitation to coherent TE2D. All techniques solved the questions for which they were constructed, but they are not limited to these cases. Especially TE2D opens new roads in photochemistry. By connecting reactant, product and the corresponding intermediates, a chemical reaction can be tracked through all stages, making unambiguous identification of the reactive states feasible. Thus, fundamental insight into the photochemistry of molecular compounds is gained.
Einzelstrang-DNA-dispergierte und individualisierte (6,5)-chirale Kohlenstoffnanoröhren bilden als Konjugatsystem den Ausgangspunkt dieser Dissertation. Im Vordergrund stehen dabei Untersuchungen zur Biokompatibilität dieser ssDNA-SWNT-Konjugate sowie deren Verhalten nach Zellpenetration und eine Funktionalisierbarkeit zum Wirkstofftransportsystem. Das erste Projekt widmet sich in Kapitel 4 dem Studium der Konjugatstabilität unter physiologischen Bedingungen und einer Verträglichkeit gegenüber zellulären Systemen. Experimente zur Biokompatibilität werden erstmals an Nanorohrkonjugaten durchgeführt, welche nach Ultrazentrifugation im Dichtegradienten sorgfältig individualisiert vorliegen. Die umgebungssensitiven photophysikalischen Charakteristika vereinzelter (6,5)-SWNTs können zu einer Beurteilung der Konjugatintegrität in physiologischem Milieu genutzt werden. Die Stabilität von ssDNA-SWNT-Strukturen wird in Anwesenheit des Restriktionsenzyms DNase I und dem in Zellnährmedien enthaltenen protein- und nukleasereichem Serum FBS auf die Probe gestellt. In beiden Fällen kann eine ausreichende ssDNA-SWNT-Integrität attestiert werden, die eine Verwendung unter Zellkultivierungsbedingungen erlaubt. Unter Berücksichtigung verschiedener in Zellen vorliegender pH-Umgebungen werden die Konjugate ebenfalls dieser Variation ausgesetzt. Bei Vorliegen stark saurer und basischer pH-Werte kann die Integrität von ssDNA-SWNT-Konjugaten nicht gewährleistet werden, was sich durch Aggregation bemerkbar macht. Innerhalb des breiten pH-Bereichs zwischen den Werten 3 und 11 hingegen kann eine gute Stabilität bestätigt werden. Für zelluläre Anwendungen bedeutet dieser Befund keine Einschränkung, da in Kulturen lediglich neutrale bis schwach saure pH-Werte oberhalb von 4.5 zu finden sind. Nachdem die Biostabilität der ssDNA-SWNT-Konjugate gewährleistet ist, kann in Zytotoxizitätsstudien eine ex vivo-Verträglichkeit des Nanomaterials getestet werden. Erste Untersuchungen mit der Mausmakrophagenlinie J774.1 weisen wie auch ausführliche Studien gegenüber menschlichen Epithelzellen HeLa auf eine uneingeschränkte Kompatibilität in den eingesetzten Konzentrationen hin. HeLa-Zellen, die mit DGU-gereinigten Nanorohrproben behandelt werden, zeigen eine geringfügig höhere Vitalität als nach Inkubation mit einer Rohdispersion undefinierter SWNT-Bündel. Im Gesamtbild ergibt sich somit eine zufriedenstellende Biokompatibilität individualisierter ssDNA-SWNT-Konjugate, womit das in dieser Arbeit zentrale Kohlenstoffnanorohrsystem den Anforderungen für dessen biomedizinische Verwendbarkeit gerecht wird. Der Schwerpunkt weiterer Untersuchungen liegt im zweiten Projekt aus Kapitel 5 auf dem Verhalten von ssDNA-SWNT-Konjugaten nach deren Aufnahme in HeLa-Zellen. Auch hier kann die starke Sensitivität der optischen Eigenschaften individualisierter (6,5)-Kohlenstoffnanoröhren gegenüber Umgebungseinflüssen genutzt werden, um Veränderungen im Emissionsverhalten von SWNTs nach deren zellulärer Aufnahme gegenüber dem Ausgangszustand zu beobachten. Nach ausführlicher Weißlicht-, Fluoreszenz- und SWNT-Photolumineszenzmikroskopie, aus deren Resultaten eine erfolgreiche Internalisierung von ssDNA-SWNTs in HeLa-Zellen eindeutig hervorgeht, stehen PL-spektroskopische Untersuchungen der Kohlenstoffnanoröhren im Vordergrund. Durch einen Vergleich des Emissionsverhaltens der ssDNA-SWNT-Konjugate in und außerhalb von Zellen können spektrale Verschiebungen, Linienverbreiterungen und verkürzte Fluoreszenzlebensdauern nach zellulärer Aufnahme festgestellt werden. Sowohl eine Aggregation von SWNTs als auch eine Beeinflussung durch die pH-Umgebung reichen nicht für eine vollständige Erklärung des Befunds aus. Vielmehr kann die in endosomalen Kompartimenten durch das Größenverhältnis von Endosomen zu SWNTs entstehende räumliche Nähe einer großen Nanorohrmenge untereinander als Ursache für eine Veränderung der dielektrischen Umgebung und folglich des Emissionsverhaltens betrachtet werden. Durch Verwendung der Kohlenstoffnanoröhren als Marker und Sensor können ssDNA-SWNT-Konjugate in Zellen somit nicht nur lokalisiert, sondern darüber hinaus hinsichtlich einer möglichen Aggregation untersucht werden. Aus den in dieser Arbeit vorgestellten Daten kann zwar eine vollständige Aggregation der SWNTs durch deren Aufnahme in Zellen ausgeschlossen werden, sie muss jedoch in geringfügigem Ausmaß neben einer Beeinflussung durch die pH-Umgebung und die große räumliche Nähe durchaus in Betracht gezogen werden. Individualisierte ssDNA-SWNT-Konjugate können damit erstmals zeitaufgelöst PL-mikrospektroskopisch in HeLa-Zellen charakterisiert werden. Für das letzte Projekt werden in Kapitel 6 neuartige Funktionalisierungsmöglichkeiten von ssDNA-SWNT-Konjugaten zu zellulären Transportsystemen unter Erhalt der photophysikalischen Eigenschaften erforscht. Dazu soll das Dispergiermittel DNA als Kupplungsstelle für eine kovalente Anbindung eines Agenz genutzt werden. Anstelle eines Wirkstoffes werden die Untersuchungen mit einem Fluorophor als Modellverbindung durchgeführt, welcher den Vorteil einer einfachen Detektierbarkeit liefert. Prinzipiell besteht die Möglichkeit, das Oligomer mit dem Fluorophor vorzufunktionalisieren und anschließend auf die Oberfläche der SWNTs zu bringen. Als effektiver erweist sich die Methode der direkten Kupplung des Farbstoffs an bereits DNA-dispergierte SWNTs. Der Erfolg in der Präparation von FluorophorssDNA- SWNT-Konjugaten wird über die Emission des Fluorophors mit entsprechenden Referenzexperimenten gemessen. Der Versuch einer Quantifizierung liefert jedoch sehr hohe Werte, die lediglich als eine obere Grenze für die gefundene Anzahl gebundener Fluorophore pro Nanoröhre angesehen werden können. Im Verlauf des Projekts kann eine Funktionalisierbarkeit der Nanoröhren über das Dispergieradditiv DNA als neue Strategie aufgezeigt werden. Im Gegensatz zu bekannten Wirkstofftransportsystemen bietet dieser Funktionalisierungsansatz den Vorteil, dass die optischen Eigenschaften der individualisierten ssDNA-SWNT-Konjugate erhalten bleiben, welche wieder um einen gleichzeitigen Einsatz der Nanoröhren als Transporter und Marker bzw. Sensor erlauben. Die vorliegende Dissertation liefert neben dieser bisher unbekannten Funktionalisierungsstrategie neue Erkenntnisse über die Biokompatibilität speziell von individualisierten ssDNA-SWNT-Konjugaten und deren Verhalten in HeLa-Zellen. Mit diesem Wissen kann der gezielte Wirkstofftransport durch Kohlenstoffnanoröhren als biokompatibles und zellgängiges Trägersystem anvisiert werden.
In this thesis, the influence of an environment on molecules and, in particular, on the quantum control of such systems is investigated. Different approaches to describe system-bath dynamics are implemented and applied. The inclusion of a dissipation term in the system Hamiltonian leads to energy loss and relaxation to the ground state. As a first application, the isomerisation reaction in an aromatic complex is treated. It is shown that this simple model is able to reproduce results of time-resolved spectroscopic measurements. Next, the influence of noise is investigated. The incorporation of fluctuations reveals that energy is not conserved and coherences are destroyed. As an example, the quantum control of a population transfer in Na2 is examined. The efficiency of control processes is studied in dependence on the strength of the noise and different system-bath couplings. Starting with the unperturbed system, Local Control Theory is applied to construct a field which selectively transfers population into a single excited electronic state. The coupling to the bath is then switched on to monitor the dependence of the coupling strength on the transfer efficiency. The perturbation of the bath effects the Na2 molecule in such a way that potential energy curves and transition dipole moments are distorted. An important result is that already elastic collisions lead to a substantial loss of control efficiency. The most promising approach used in this thesis is the stochastic Schrödinger equation. It is equivalent to the commonly employed descriptions of system-bath dynamics within the reduced density matrix formalism. It includes decoherences and dissipation caused by elastic and inelastic collisions. Our contribution is the incorporation of laser excitation into the kinetic Monte-Carlo scheme. Thus we are able to apply this stochastic approach to the quantum control of population transfer in the sodium dimer. Because within our description it is possible to separate pure dephasing, inelastic transitions, and coherent time-evolution, we can identify the relative influence of these processes on the control efficiency. This leads to a far more physical picture of the basic processes underlying the perturbations of an environment then what a reduced density matrix description can provide. In utilising the stochastic wave function approach instead of the density matrix formalism, the computations are quite efficient. The stochastic Schrödinger equation is realised by N independent runs, where, in our case, an ensemble size of N = 1000 gives converged results. The efficiency of the laser control process is studied as a function of temperature and collision rates. A rise in temperature (or collision rate) reeffects a stronger fluctuation and thus results in a less efficient transfer by the control field. Though the Gaussian fluctuations used here do not strictly represent 'white'- noise, since a deterministic machine is not able to produce uncorrelated random numbers, an acceptable distribution is achieved by simple procedures. An improvement of the here applied algorithms would, for instance, include a more sophisticated sampling of the dephasing rates. Only one example of a control process is studied here and an application of the developed approach to other problems of quantum control is to be performed. This thesis established a systematic approach to understand quantum control in the presence of an environment.
Investigation of Nanostructure-Induced Localized Light Phenomena Using Ultrafast Laser Spectroscopy
(2017)
In recent years, the interaction of light with subwavelength structures, i.e., structures that are smaller than the optical wavelength, became more and more interesting to scientific research, since it provides the opportunity to manipulate light-induced dynamics below the optical diffraction limit. Specifically designed nanomaterials can be utilized to tailor the temporal evolution of electromagnetic fields at the nanoscale. For the investigation of strongly localized processes, it is essential to resolve both their spatial and their temporal behavior. The aim of this thesis was to study and/or control the temporal evolution of three nanostructure-induced localized light phenomena by using ultrafast laser spectroscopy with high spatial resolution.
In Chapter 4, the absorption of near-infrared light in thin-film a-Si:H solar cells was investigated. Using nanotextured instead of smooth interfaces for such devices leads to an increase of absorption from < 20% to more than 50% in the near-infrared regime. Time-resolved experiments with femtosecond laser pulses were performed to clarify the reason for this enhancement. The coherent backscattered radiation from nanotextured solar cell devices was measured as a function of the sample position and evaluated via spectral interferometry. Spatially varying resonance peaks in the recorded spectra indicated the formation of localized photonic modes within the nanotextured absorber layers. In order to identify the modes separately from each other, coherent two-dimensional (2D) nanoscopy was utilized, providing a high spatial resolution < 40 nm. In a nanoscopy measurement on a modified device with an exposed nanotextured a-Si:H absorber layer, hot-spot electron emission was observed and confirmed the presence of localized modes. Fitting the local 2D nanospectra at the hot-spot positions enabled the determination of the resonance frequencies and coherence lifetimes of the modes. The obtained lifetime values varied between 50 fs and 130 fs. Using a thermionic emission model allowed the calculation of the locally absorbed energy density and, with this, an estimation of the localization length of the photonic modes (≈1 μm). The localization could be classified by means of the estimated localization length and additional data evaluation of the backscattered spectra as strong localization ─ the so-called Anderson localization.
Based on the experimental results, it was concluded that the enhanced absorption of near-infrared light in thin-film silicon solar cells with nanotextured interfaces is caused by the formation of strongly localized photonic modes within the disordered absorber layers. The incoming near-infrared light is trapped in these long-living modes until absorption occurs.
In Chapter 5, a novel hybridized plasmonic device was introduced and investigated in both theory and experiment. It consists of two widely separated whispering gallery mode (WGM) nanoantennas located in an elliptical plasmonic cavity. The goal was to realize a periodic long-range energy transfer between the nanoantennas. In finite-difference time-domain (FDTD) simulations, the device was first optimized with respect to strong coupling between the localized antenna modes and the spatially-extended cavity mode. The geometrical parameters of the antennas and the cavity were adjusted separately so that the m="0" antenna mode and the cavity mode were resonant at λ="800 nm" . A high spatial overlap of the modes was achieved by positioning the two antennas in the focal spots of the cavity, leading to a distance between the antenna centers of more than twice the resonant wavelength of the modes. The spectral response of the optimized device revealed an energy splitting of the antenna and the cavity mode into three separated hybridized eigenmodes within an energy range of about 90 meV due to strong coupling. It could be well reproduced by a simple model of three coupled Lorentzian oscillators. In the time domain, an oscillatory energy transfer between both antennas with a period of 86 fs and an energy transfer efficiency of about 7% was observed for single-pulse excitation. For the experiments, devices with cavities and antennas of varying size were fabricated by means of focused-ion-beam (FIB) milling. Time-resolved correlation measurements were performed with high spatial and temporal resolution by using sequences of two femtosecond laser pulses for excitation and photoemission electron microscopy (PEEM) for detection. Local correlation traces at antennas in resonant devices, i.e., devices with enhanced electron emission at both antenna positions, were investigated and reconstructed by means of the coupled-oscillator model. The corresponding spectral response revealed separated peaks, confirming the formation of hybridized eigenmodes due to strong coupling. In a subsequent simulation for single-pulse excitation, one back-and-forth energy transfer between both antennas with an energy transfer efficiency of about 10% was observed.
Based on the theoretical and experimental results, it was demonstrated that in the presented plasmonic device a periodic long-range energy transfer between the two nanoantennas is possible. Furthermore, the coupled-oscillator model enables one to study in depth how specific device properties impact the temporal electric-field dynamics within the device. This can be exploited to further optimize energy transfer efficiency of the device. Future applications are envisioned in ultrafast plasmonic nanocircuitry. Moreover, the presented device can be employed to realize efficient SPP-mediated strong coupling between widely separated quantum emitters.
In Chapter 6, it was investigated in theory how the local optical chirality enhancement in the near field of plasmonic nanostructures can be optimized by tuning the far-field polarization of the incident light. An analytic expression was derived that enables the calculation of the optimal far-field polarizations, i.e., the two far-field polarizations which lead to the highest positive and negative local optical chirality, for any given nanostructure geometry. The two optimal far-field polarizations depend on the local optical response of the respective nanostructure and thus are functions of both the frequency ω and the position r. Their ellipticities differ only in their sign, i.e., in their direction of rotation in the time domain, and the angle between their orientations, i.e., the angle between the principal axes of their ellipses, is ±π/"2" . The handedness of optimal local optical chirality can be switched by switching between the optimal far-field polarizations. In numerical simulations, it was exemplarily shown for two specific nanostructure assemblies that the optimal local optical chirality can significantly exceed the optical chirality values of circularly polarized light in free space ─ the highest possible values in free space. The corresponding optimal far-field polarizations were different from linear and circular and varied with frequency. Using femtosecond polarization pulse shaping provides the opportunity to coherently control local optical chirality over a continuous frequency range. Furthermore, symmetry properties of nanostructures can be exploited to determine which far-field polarization is optimal.
The theoretical findings can have impact on future experimental studies about local optical chirality enhancement. Tuning the far-field polarization of the incident light offers a promising tool to enhance chirally specific interactions of local electromagnetic fields with molecular and other quantum systems in the vicinity of plasmonic nanostructures. The presented approach can be utilized for applications in chiral sensing of adsorbed molecules, time-resolved chirality-sensitive spectroscopy, and chiral quantum control.
In conclusion, each of the localized light phenomena that were investigated in this thesis ─ the enhanced local absorption of near-infrared light due to the formation of localized photonic modes, the periodic long-range energy transfer between two nanoantennas within an elliptical plasmonic cavity, and the optimization of local optical chirality enhancement by tuning the far-field polarization of the incident light ─ can open up new perspectives for a variety of future applications.
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Polarisations-sensitive Resonanz-CARS- und Resonanz-Raman-Spektroskopie an metallfreien Porphyrinen
(2006)
Es werden in dieser Arbeit Raman-spektroskopische Untersuchungen an metallfreien Porphyrinen in verdünnter Lösung vorgestellt. Dabei werden Laseranregungswellenlängen eingesetzt, die mit elektronischen Resonanzen der Porphyrine zusammenfallen. Die Ausnutzung von Resonanz-Effekten hat zum einen den Vorteil, dass gewisse Raman-Banden, je nach der Symmetrie der zugrunde liegenden Molekülschwingung, eine deutliche Intensitätsverstärkung erfahren können, was den Nachweis auch geringer Probenkonzentrationen ermöglicht. Zum anderen sind anhand der Banden-Parameter Rückschlüsse auf die exakte Molekülsymmetrie möglich. Im Vergleich zu Metalloporphyrinen sind für metallfreie Porphyrine bisher nur wenige Daten aus resonanten Raman-Spektren bekannt. Ein Grund hierfür ist, dass letztere ein höheres Maß an Fluoreszenz zeigen, die die Raman-Signale überlagert. Während bei Laseranregungen im Bereich hochenergetischer elektronischer Absorptionen der Porphyrine (B-Banden-Region) die klassische spontane Raman-Spektroskopie noch angewendet werden kann, ist dies im Bereich niederenergetischer Absorptionen (Q-Banden-Region) meist nicht mehr möglich. Um auch Anregungen in der Q-Banden-Region zu verwirklichen, wird daher in dieser Arbeit von der kohärenten anti-Stokesschen Raman-Streuung (coherent anti-Stokes Raman scattering, CARS) Gebrauch gemacht. Die CARS-Spektroskopie ermöglicht es, das Fluoreszenzproblem zu umgehen, und bietet zudem noch weitere Vorteile, z. B. bezüglich der Unterscheidbarkeit spektral benachbarter Banden sowie bezüglich der Bestimmung symmetrierelevanter Parameter. Raman-Banden-Parameter aus Q-Banden-CARS-Spektren konnten hier für vier metallfreie Porphyrine, die sich im Substitutionsmuster an den beta-Kohlenstoffatomen des Tetrapyrrol-Makrozyklus unterscheiden, erhalten werden. Die CARS-Parameter, in Kombination mit Parametern aus spontanen B-Banden-Raman-Spektren sowie mit quantenchemisch berechneten Schwingungsvektoren, ließen den Schluss zu, dass Symmetrieunterschiede zwischen den Makrozyklen dieser Moleküle zwar gering, aber durchaus feststellbar sind. Desweiteren konnten durch die niederenergetische Anregung für die metallfreien Porphyrine spezifische Resonanzeffekte nachgewiesen werden, die z. T. von den für Metalloporphyrine bekannten Mustern abweichen.
Electrophilic (het)arenes can undergo reactions with nucleophiles yielding π- or Meisenheimer (σ-) complexes or the products of the S\(_N\)Ar addition/elimination reactions. Such building blocks have only rarely been employed for the design of enzyme inhibitors. Herein, we demonstrate the combination of a peptidic recognition sequence with such electrophilic (het)arenes to generate highly active inhibitors of disease-relevant proteases. We further elucidate an unexpected mode of action for the trypanosomal protease rhodesain using NMR spectroscopy and mass spectrometry, enzyme kinetics and various types of simulations. After hydrolysis of an ester function in the recognition sequence of a weakly active prodrug inhibitor, the liberated carboxylic acid represents a highly potent inhibitor of rhodesain (K\(_i\) = 4.0 nM). The simulations indicate that, after the cleavage of the ester, the carboxylic acid leaves the active site and re-binds to the enzyme in an orientation that allows the formation of a very stable π-complex between the catalytic dyad (Cys-25/His-162) of rhodesain and the electrophilic aromatic moiety. The reversible inhibition mode results because the S\(_N\)Ar reaction, which is found in an alkaline solvent containing a low molecular weight thiol, is hindered within the enzyme due to the presence of the positively charged imidazolium ring of His-162. Comparisons between measured and calculated NMR shifts support this interpretation
The facile synthesis and detailed investigation of a class of highly potent protease inhibitors based on 1,4-naphthoquinones with a dipeptidic recognition motif (HN-l-Phe-l-Leu-OR) in the 2-position and an electron-withdrawing group (EWG) in the 3-position is presented. One of the compound representatives, namely the acid with EWG = CN and with R = H proved to be a highly potent rhodesain inhibitor with nanomolar affinity. The respective benzyl ester (R = Bn) was found to be hydrolyzed by the target enzyme itself yielding the free acid. Detailed kinetic and mass spectrometry studies revealed a reversible covalent binding mode. Theoretical calculations with different density functionals (DFT) as well as wavefunction-based approaches were performed to elucidate the mode of action.
In this thesis, several contributions to the understanding and modeling of chemical phenomena using computational approaches are presented. These investigations are characterized by the usage of non-standard computational modeling techniques, which is necessitated by the complex nature of the electronic structure or atomic fluctuations of the target molecules.
Multiple biradical-type molecules and their spectroscopic properties were modeled. In the course of the investigation, it is found that especially the impact of correct molecular geometries on the computationally predicted absorption properties may be critical. In order to find the correct minimum geometries, Multi-Reference methods may have to be invoked.
The impact of geometry relaxation on the excitonic properties of Perylene Bisimide dimers were investigated. Oftentimes, these geometry factors are neglected in Organic Semiconductor modeling as an approximation. This present investigation suggests that this approximation is not always valid, as certain regimes are identified where geometrical parameters have critical impact on the localization and energetic properties of excitons.
The mechanism of the Triazolinedione (TAD) tyrosine bioconjugation reaction is investigated using quantum-chemical methods. By comparison of different conceivable mechanisms and their energetic ordering, the TAD tyrosine bioconjugation is found to proceed by means of a base-mediated electrophilic aromatic substitution reaction.
The kth nearest neighbor entropy estimation protocol is investigated. This estimator promises accurate entropy estimates even for flexible molecules with multiple structural minima. Our granular investigation of formal and practical properties of the estimator suggests that the uneven variance of a molecule’s vibrational modes is the cause of the observed slow convergence of the estimator. A rescaling procedure to reestablish fast convergence is suggested and benchmarks are performed.
Theory and simulation of ultrafast autodetachment dynamics and nonradiative relaxation in molecules
(2024)
In this thesis, theoretical approaches for the simulation of electron detachment processes in molecules following vibrational or electronic excitation are developed and applied. These approaches are based on the quantum-classical surface-hopping methodology, in which nuclear motion is treated classically as an ensemble of trajectories in the potential of quantum-mechanically described electronic degrees of freedom.
The photoionization of several nitrogen-containing reactive intermediates relevant in combustion processes was investigated in the gas phase employing VUV synchrotron radiation. The intermediates were either freshly prepared and stored under cryogenic temperatures during the experiment or generated in situ by vacuum flash pyrolysis of suitable precursor molecules. The iPEPICO (imaging photoelectron photoion coincidence) setups of the VUV beamlines at the Swiss Light Source and Synchrotron SOLEIL were then used to record mass-selected threshold photoelectron (TPE) spectra. TPE spectra reveal the ionization energy and vibrational structure in the cationic states can often be resolved, which enables to distinguish different isomers. Accurate ionization energies for the radicals carbonyl amidogen, pyrrolyl, and 3-picolyl, and for the closed shell molecules isocyanic acid and cyanovinylacetylene were obtained. The analysis of the dissociative photoionization of the pyrolysis precursors enables in some cases to retrieve thermochemical data. Beyond, the absolute photoionization cross section of the cyclic carbene cyclopropenylidene was determined, NEXAFS and normal Auger spectra of isocyanic acid were recorded and analyzed at the O1s, N1s, and C1s edges, and the dissociative photoionization and pyrolysis of 1,4-di-tert-butyl-1,4-azaborinine was studied.
We report infrared spectra of xylylene isomers in the gas phase, using free electron laser (FEL) radiation. All xylylenes were generated by flash pyrolysis. The IR spectra were obtained by monitoring the ion dip signal, using a IR/UV double resonance scheme. A gas phase IR spectrum of para‐xylylene was recorded, whereas ortho‐ and meta‐xylylene were found to partially rearrange to benzocyclobutene and styrene. Computations of the UV oscillator strength for all molecules were carried out and provde an explanation for the observation of the isomerization products.
Die vorliegende Dissertation untersucht fünf unterschiedliche Moleküle hinsichtlich ihrer Geometrien im Grund- und angeregten Zustand sowie deren Dynamik
nach elektronischer Anregung. Der Fokus liegt dabei unter anderem auf Pi-konjugierten Systemen, die über eine zusätzliche aliphatische Einheit verbrückt (Paracyclophan-
Derivate) oder erweitert (Pyracen) sind. Die Paracyclophan-Derivate sind ein ideales Modellsystem um Einsicht in Pi-Pi-Wechselwirkungen zu erlangen. Ein
weiterer Schwerpunkt dieser Arbeit beschreibt die Dynamik des resonanzstabilisierten 2-Methylallyl-Radikals. Die Forschung an solchen kleinen Kohlenwasserstoff-Radikalen ist wichtig, da auf deren Grundlage Modelle entwickelt werden können, die zum Beispiel helfen, den Verbrennungsprozess aufzuklären. Aufgrund ihrer Instabilität sind solche kleinen Kohlenwasserstoff-Radikale nicht einfach zu handhaben und das spektroskopische Vermessen stellt immer eine Herausforderung dar.
This work aims at elucidating chemical processes involving homogeneous catalysis and photo–physical relaxation of excited molecules in the solid state. Furthermore, compounds with supposedly small singlet–triplet gaps and therefore biradicaloid character are investigated with respect to their electro–chemical behavior. The work on hydroboration catalysis via a reduced 9,10–diboraanthracene (DBA) was preformed in collaboration with the Wagner group in Frankfurt, more specifically Dr. Sven Prey, who performed all laboratory experiments. The investigation of delayed luminescence properties in arylboronic esters in their solid state was conducted in collaboration with the Marder group in Würzburg. The author of this work took part in the synthesis of the investigated compounds while being supervised by Dr. Zhu Wu. The final project was a collaboration with the group of Anukul Jana from Hyderabad, India who provided the experimental data.
Die vorliegende Dissertation untersucht reaktive Intermediaten, speziell Radikale und Carbene und deren Verhalten bei Photoionisation mit VUV-Synchrotronstrahlung. Diese instabilen Verbindungen wurden durch Pyrolyse von teils selbstsynthetisierter Vorläufern in einem kontinuierlichen Molekularstrahl erzeugt und mittels der TPEPICO-Spektroskopie untersucht. Die wichtigsten Ergebnisse dieser Arbeit werden im Anschluss hervorgehoben. Drei Radikale der Zusammensetzung C9H7, Indenyl, 1- und 3-Phenylpropargyl wurden aus ihren bromierten Vorläufern synthetisiert und ihre Ionisierungsenergien bestimmt. Die Frage ob es möglich ist alle drei Radikale hinsichtlich ihrer IE zu unterscheiden und dadurch eine Identifikation in einer Flamme möglich wird, konnte beantwortet werden. Indenyl und 3-Phenylpropargyl besitzen Ionisierungsenergien von 7.53 und 7.20 eV, was eine Erkennung in Flammen prinzipiell möglich macht. Für 1-Phenylpropargyl wurde eine IEad von 7.4 eV gemessen, was eine selektive Identifikation erschwert. Die Messwerte wurden durch quantenchemischen Rechnungen überprüft und sind mit diesen in guter Übereinstimmung. Die Photoionisation von Cyclopropenyliden (IEad = 9.17 ± 0.015 eV) wurde untersucht,wobei eine niederenergetische Bande dem Propargylen (IEad = 9.02 ± 0.02 eV), dem HCCCH Isomer der Zusammensetzung C3H2, zugeordnet werden konnte. Die Schwingungsstruktur des Spektrums konnte erfolgreich simuliert und dadurch die Geometrie des Kations ermittelt werden. Als Nebenprodukt im Molekularstrahl wurde Chlorcyclopropenyliden (IEad = 9.17 ± 0.02 eV) durch seine Schwingungsprogression identifiziert. Die Analyse der dissoziativen Photoionisation gestaltet sich als schwierig, da sowohl c-C3H2 als auch c-C3HCl im relevanten Energiebereich fragmentieren können und die Anwesenheit von HCl die Auswertung ebenfalls erschwert. Ein Lösungsvorschlag für dieses Problem wurde ebenfalls aufgezeigt. Der Einfluss von Substitutionen auf die IE wurde am Beispiel des Propargylradikals und seiner zwei bromierten Analoga erforscht. Dabei wurde eine Rotverschiebung (IEad(C3H3) = 8.71 ± 0.02 eV / IEad(BrCCCH2) = 8.16 ± 0.02 eV / IEad(BrHCCCH) = 8.34 ± 0.02 eV) gemessen. Diese ist auf den elektronenspendenden Charakter des Broms begründet. Beide Brompropargylradikale lassen sich anhand ihrer IE unterscheiden. Die Schwelle zur dissoziativen Photoionisation von C3H2Br zu C3H2 wurde mit 10.1 eV ermittelt, wobei verschiedene Kanäle für diese Reaktion in Frage kommen. Schwingungsaktivität konnte im TPE-Spektrum des Propargylradikals ebenfalls verzeichnet und die v3 +-Mode mit 1950 cm-1 ermittelt werden. Als letztes Projekt stand die Photoionisation des t-Butyl im Fokus, da teils widersprüchliche Messwerte für die IEad in der Literatur publiziert sind. Es konnte ein Wert von 6.75 eV ± 0.03 eV gemessen werden. Die Schwierigkeit bei diesem Experiment ist die Geometrieänderung während der Ionisierung, da das Radikal pyramidal und das Kation eine planare Struktur im C-Gerüst besitzt. Die Grenzen der angewendeten Methoden wurden an diesem Beispiel deutlich gemacht. Zur vollständigen Charakterisierung wurden auch die Vorläufer genau analysiert, da diese durch dissoziative Photoionisation (DPI) Fragmentionen bilden, welche die gleiche Masse besitzen wie die zu untersuchenden Radikale und Carbene. Aus diesen Ergebnissen konnten Bindungsenergien berechnet werden. Von allen untersuchten reaktiven Intermediaten konnten die Ionisierungsenergien mit einer Genauigkeit von ± 20 meV ermittelt werden. Es wurde gezeigt, dass sogar Isomere mit gleicher Molekülmasse unterscheidbar sind. Diese Daten lassen sich verwenden um reaktive Zwischenprodukte in Flammen zu identifizieren. Die Identifizierung ermöglicht es dann geeignete Modelle für Verbrennungsprozesse zu konstruieren oder vorhandene zu verbessern. Diese könnten wiederum helfen die Ruß- und PAK-Bildung besser zu verstehen. Die Ziele dieser Dissertation konnten somit erreicht werden. Massenspektren, welche in Flammen durch VUV-Synchrotronstrahlung aufgenommen wurden, beherbergen eine große Fülle an größeren reaktiven Intermediaten wie beispielsweise das Fluorenyl oder das Biphenylmethylradikal. Deren Ionisation ist bislang nur sehr vage erforscht und wäre deshalb ein interessantes Projekt um diese Arbeit fortzuführen.
Mechanistic Insights into the Inhibition of Cathepsin B and Rhodesain with Low-Molecular Inhibitors
(2019)
Cysteine proteases play a crucial role in medical chemistry concerning various fields reaching from more common ailments like cancer and hepatitis to less noted tropical diseases, namely the so-called African Sleeping Sickness (Human Arfican Trypanosomiasis). Detailed knowledge about the catalytic function of these systems is highly desirable for drug research in the respective areas. In this work, the inhibition mechanisms of the two cysteine proteases cathepsin B and rhodesain with respectively one low-molecular inhibitor class were investigated in detail, using computational methods. In order to sufficiently describe macromolecular systems, molecular mechanics based methods (MM) and quantum mechanical based method (QM), as well as hybrid methods (QM/MM) combining those two approaches, were applied.
For Cathespin B, carbamate-based molecules were investigated as potential inhibitors for the cysteine protease. The results indicate, that water-bridged proton-transfer reactions play a crucial role for the inhibition. The energetically most favoured pathway (according to the calculations) includes an elimination reaction following an E1cB mechanism with a subsequent carbamylation of the active site amino acid cysteine.
Nitroalkene derivatives were investigated as inhibitors for rhodesain. The investigation of structurally similar inhibitors showed, that even small steric differences can crucially influence the inhibition potential of the components. Furthermore, the impact of a fluorination of the nitroalkene inhibitors on the inhibition mechanism was investigated. According to experimental data measured from the working group of professor Schirmeister in Mainz, fluorinated nitroalkenes show – in contrast to the unfluorinated compounds – a time dependent inhibition efficiency. The calculations of the systems indicate, that the fluorination impacts the non-covalent interactions of the inhibitors with the enzymatic environment of the enzyme which results in a different inhibition behaviour.