@phdthesis{Spenst2017, author = {Spenst, Peter}, title = {Xylylene Bridged Perylene Bisimide Cyclophanes and Macrocycles}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-139015}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2017}, abstract = {This work is concerned with the syntheses and photophysical properties of para-xylylene bridged macrocycles nPBI with ring sizes from two to nine PBI units, as well as the complexation of polycyclic aromatic guest compounds. With a reduced but substantial fluorescence quantum yield of 21\% (in CHCl3) the free host 2PBI(4-tBu)4 can be used as a dual fluorescence probe. Upon encapsulation of rather electron-poor guests the fluorescence quenching interactions between the chromophores are prevented, leading to a significant fluorescence enhancement to > 90\% ("turn-on"). On the other hand, the addition of electron-rich guest molecules induces an electron transfer from the guest to the electron-poor PBI chromophores and thus quenches the fluorescence entirely ("turn-off"). The photophysical properties of the host-guest complexes were studied by transient absorption spectroscopy. These measurements revealed that the charge transfer between guest and 2PBI(4-tBu)4 occurs in the "normal region" of the Marcus-parabola with the fastest charge separation rate for perylene. In contrast, the charge recombination back to the PBI ground state lies far in the "inverted region" of the Marcus-parabola. Beside complexation of planar aromatic hydrocarbons into the cavity of the cyclophanes an encapsulation of fullerene into the cyclic trimer 3PBI(4-tBu)4 was observed. 3PBI(4-tBu)4 provides a tube-like structure in which the PBI subunits represent the walls of those tubes. The cavity has the optimal size for hosting fullerenes, with C70 fitting better than C60 and a binding constant that is higher by a factor of 10. TA spectroscopy in toluene that was performed on the C60@3PBI(4-tBu)4 complex revealed two energy transfer processes. The first one comes from the excited PBI to the fullerene, which subsequently populates the triplet state. From the fullerene triplet state a second energy transfer occurs back to the PBI to generate the PBI triplet state. In all cycles that were studied by TA spectroscopy, symmetry-breaking charge separation (SB-CS) was observed in dichloromethane. This process is fastest within the PBI cyclophane 2PBI(4-tBu)4 and slows down for larger cycles, suggesting that the charge separation takes place through space and not through bonds. The charges then recombine to the PBI triplet state via a radical pair intersystem crossing (RP-ISC) mechanism, which could be used to generate singlet oxygen in yields of ~20\%. By changing the solvent to toluene an intramolecular folding of the even-numbered larger cycles was observed that quenches the fluorescence and increases the 0-1 transition band in the absorption spectra. Force field calculations of 4PBI(4-tBu)4 suggested a folding into pairs of dimers, which explains the remarkable odd-even effect with respect to the number of connected PBI chromophores and the resulting alternation in the absorption and fluorescence properties. Thus, the even-numbered macrocycles can fold in a way that all chromophores are in a paired arrangement, while the odd-numbered cycles have open conformations (3PBI(4-tBu)4, 5PBI(4-tBu)4, 7PBI(4-tBu)4) or at least additional unpaired PBI unit (9PBI(4-tBu)4). With these experiments we could for the first time give insights in the interactions between cyclic PBI hosts and aromatic guest molecules. Associated with the encapsulation of guest molecules a variety of possible applications can be envisioned, like fluorescence sensing, chiral recognition and photodynamic therapy by singlet oxygen generation. Particularly, these macrocycles provide photophysical relaxation pathways of PBIs, like charge separation and recombination and triplet state formation that are hardly feasible in monomeric PBI dyes. Furthermore, diverse compound specific features were found, like the odd-even effect in the folding process or the transition of superficial nanostructures of the tetrameric cycle influenced by the AFM tip. The comprehensive properties of these macrocycles provide the basis for further oncoming studies and can serve as an inspiration for the synthesis of new macrocyclic compounds.}, subject = {Supramolekulare Chemie}, language = {en} } @phdthesis{Dobrawa2004, author = {Dobrawa, Rainer Anton}, title = {Synthesis and characterization of terpyridine-based fluorescent coordination polymers}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-10367}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2004}, abstract = {Complexation properties of 2,2':6',2''-terpyridine (tpy) have been studied with a series of first row transition metal ions by UV-vis, 1H NMR and isothermal titration calorimetry and ƒ´H values for the tpy complexation processes have been determined. These studies reveal that Zn2+ is the best suited metal ion for the reversible coordination of the terpyridine ligand. Thus, supramolecular coordination polymerization of perylene bisimide fluorophores containing terpyridine functionalities have been investigated by using Zn2+ as metal ion. The formation of the dimeric complexes in the case of monotopic model comounds and coordination polymerization of ditopic functional building blocks have been confirmed by 1H NMR studies. The optical properties of dimeric and polymeric complexes have been investigated by UV-vis and fluorescence spectroscopy. The Zn2+ coordination to the terpyridine unit does not effect the advantageous fluorescence properties of perylene bisimide moieties. The reversibility of the formation of coordination polymers has been established by 1H NMR and additionally by DOSY NMR and fluorescence anisotropy measurements. Coordination polymer strands can be visualized by atomic force microscopy (AFM), which also reveals the formation of an ordered monolayer film at higher concentration. The average polymer length has been determined by AFM to 15 repeat units, which correlates well with the value estimated by 1H NMR to >10 repeat units.}, subject = {Terpyridinderivate <2}, language = {en} } @phdthesis{Rehm2015, author = {Rehm, Stefanie}, title = {Spermine-functionalized Perylene Bisimide Dyes: Synthesis and Self-assembly in Water}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-123201}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2015}, abstract = {The main objective of this thesis was the design and synthesis of perylene bisimide dyes with sufficient water-solubility for the construction of self-assembled architectures in aqueous solutions. Beside these tasks another goal of this project was the control over the self-assembly process in terms of aggregate size and helicity, respectively. Within this thesis an appropriate synthesis for spermine-functionalized perylene bisimide dyes was developed and conducted successfully. The characterization of these building blocks and their course of self-assembly were investigated by NMR, UV/Vis and fluorescence spectroscopy as well as by atomic force and transmission electron microscopy. For the better understanding of the experimental results theoretical calculations were performed.}, subject = {Perylenderivate}, language = {en} } @phdthesis{Stepanenko2008, author = {Stepanenko, Vladimir}, title = {Self-Assembly of Bay-Substituted Perylene Bisimide by Ligand-Metal Ion Coordination}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-32063}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2008}, abstract = {The subject of this thesis is the synthesis and characterization of PBI-based fluorescent metallosupramolecular polymers and cyclic arrays. Terpyridine receptor functionalized PBIs of predesigned geometry have been used as building blocks to construct desired macromolecular structures through metal-ion-directed self-assembly. These metallosupramolecular architectures have been investigated by NMR, UV/Vis and fluorescence spectroscopy, mass spectrometry, and atomic force microscopy.}, subject = {Supramolekulare Chemie}, language = {en} } @phdthesis{Berberich2012, author = {Berberich, Martin}, title = {Rylene Bisimide-Diarylethene Photochromic Systems for Non-Destructive Memory Read-out}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-73517}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2012}, abstract = {Diese Doktorarbeit zeigt deutlich verbesserte aus Rylenbisimiden und Diarylethenen aufgebaute, photochrome Systeme f{\"u}r das nicht-destruktive Auslesen von Fluoreszenz. Dabei wird die Fluoreszenz der Emittereinheit durch photoinduzierten Elektronentransfer nur zu einer isomeren Form des Photochromes gel{\"o}scht. Die Triebkraft f{\"u}r den Fluoreszenz-l{\"o}schenden Elektronentransfer wurde mittels Rehm-Weller-Gleichung berechnet. Die erhaltenen Systeme erf{\"u}llen die notwendigen Anforderungen f{\"u}r ein nicht-destruktives Auslesen in einem auf Schreiben, Auslesen und L{\"o}schen basierenden fluoreszierenden Datenspeicher.}, subject = {Photochromie}, language = {en} } @phdthesis{Fimmel2015, author = {Fimmel, Benjamin}, title = {Perylene Bisimide Foldamers: Synthesis and In-Depth Studies of the Ground- and Excited States Properties}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-125173}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2015}, abstract = {In this thesis the syntheses and detailed investigations on two foldable PBI systems were presented. The reversible, solvent-dependet folding/unfolding-behavior was used to study the ground and excited states properties of folda-dimer and folda-trimer by means of different spectroscopic methods as well as theoretical studies. The switching between charge transfer or excimer formation pathways of photoexcited molecules influenced by the spatial arrangement of chromophores within defined dye systems illustrates the impact of conformational preferences on functional properties.}, subject = {Perylenbisdicarboximide }, language = {en} } @phdthesis{Osswald2007, author = {Osswald, Peter Uwe}, title = {Perylene Bisimide Atropisomers : Synthesis and Optical and Chiroptical Properties}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-23248}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2007}, abstract = {Zur Herstellung von atropo-enantiomeren Perylenbisimiden wurde die kovalente Verkn{\"u}pfung von Aryloxysubstituenten durch Makrocyclisierung eingesetzt. Die Darstellung makrocyclischer Perylenbisimide erfolgte ausgehend von einem vierfach (3-Hydroxyphenoxy)-funktionalisierten Perylenbisimid mit achiralen 2,6-Diisopropylphenylsubstituenten an den Imidpositionen durch Williamsonsche Ethersynthese. Die Synthese konnte f{\"u}r vier unterschiedliche Oligoethylenglykol-Kettenl{\"a}ngen realisiert werden, wobei f{\"u}r jede Br{\"u}ckenl{\"a}nge jeweils zwei regioisomere Makrocyclen, n{\"a}mlich das diagonal verbr{\"u}ckte (1,7- und 6,12-Verk{\"u}pfung) und das seitlich verbr{\"u}ckte Isomer (1,12- und 6,7- Verkn{\"u}pfung), isoliert werden konnten. Die strukturelle Zuordnung der isolierten Makrocyclen zu einem der beiden Regioisomeren gelang zweifelsfrei anhand von R{\"o}ntgenstrukturanalysen f{\"u}r zwei Makrocyclen und 1H NMR-Spektroskopie f{\"u}r alle Isomere. Der konformative Einfluß der Aryloxy-Substituenten auf die funktionenellen Eigenschaften dieser Farbstoffklasse konnte durch Vergleich der optischen und elektrochemischen Eigenschaften aller isolierter Makrocyclen mit einer offenkettigen Referenzverbindung abgeleitet werden. Hierbei zeigte sich, dass die Aryloxy-Substituenten dieser Farbstoffe in L{\"o}sung bevorzugt in einer horizontalen Konformation vorliegen. Durch l{\"o}sungsmittelabh{\"a}ngige Fluoreszenzmessungen konnte gezeigt werden, dass ein photoinduzierter Elektronentransferprozess f{\"u}r die Fluoreszenzl{\"o}sung elektronenreicher Aryloxy-Substituenten von Bedeutung ist. Die Trennung der Atropo-Diastereomere konnte f{\"u}r eine diagonal {\"u}berbr{\"u}ckte makrocyclische Verbindung mit chiralen 2-(R)-Octylamin Imidsubstituenten und Diethyleneglykol als Br{\"u}ckenkette mittels semi-preparativer HPLC an einer chiralen station{\"a}ren Phase realisiert werden. Die chiroptischen Eigenschaften der isolierten epimerenreinen Makrocyclen wurden mittels CD-Spektroskopie untersucht. Die Zuordnung der absoluten Stereochemie konnte anhand der erhaltenen CD-Spektren durch Anwendung der „Theorie der excitonischen Kopplung" abgeleitet und durch quantenchemische Berechnung der CD-Spektren best{\"a}tigt werden. Dieses Synthesekonzept wurde auf 1,7-diaryloxy-substituierten Perylenbisimide erweitert. Die Struktur der erhaltenen diagonal verbr{\"u}ckten monocyclischen Verbindung konnte erneut durch NMR-Spektroskopie und R{\"o}ntgenstrukturanalyse eindeutig bestimmt werden. Die Trennung der Atropo-Enantiomere gelang mittels semi-preparativer HPLC an einer chiralen station{\"a}ren Phase. Die Zuordnung der Stereochemie konnte anhand des Vergleichs der CD-Spektren mit den zuvor f{\"u}r epimerenreine Bismakrocyclen erhaltenen CD-Spektren realisiert werden. Anhand der R{\"o}ntgenstrukturanalysen sowohl der racemischen Mischung als auch eines Atropo-Enantiomers ließen sich bedeutende Informationen {\"u}ber die p-Dimerisierung von Perylenbisimiden ableiten. Die Abh{\"a}ngigkeit der Razemisierungsbarriere von der Gr{\"o}ße der Bay-Substituenten wurde f{\"u}r vier halogensubstituierte Derivate untersucht. Die dynamischen Eigenschaften wurden mittels temperaturabh{\"a}ngiger NMR-Spektroskopie und kinetischer Messungen mittels CD-Spektroskopie bestimmt. Unter Anwendung des „Apparent Overlap"-Konzeptes konnte eine {\"u}berzeugende lineare Beziehung zwischen der Gr{\"o}ße der Substituenten und der Inversionsbarriere hergestellt werden. Dar{\"u}ber hinaus war es m{\"o}glich die Atropo-Diastereomere bzw. Enantiomere der tetrachlor- und tetrabrom-substituierten Derivate zu trennen, wobei vor allem das 1,6,7,12-tetrabrom-substituierte Perylenbisimid stabile Enantiomere bei Raumtemperatur lieferte. Die abgeleitete Struktur-Eigenschaftsbeziehung sollte zuk{\"u}nftig die Herstellung von stabilen Enantiomeren durch geeignete Wahl der Substituenten in den Bay-Positionen erm{\"o}glichen. Um die Reversibilit{\"a}t der Selbstorganisation zur quantitativen Synthese makrocyclischer Perylenbisimide ausn{\"u}tzen zu k{\"o}nnen, wurde ein tetra(zinkporphyrin)-funktionalisiertes Perylenbisimid synthetisiert. Die Ausbildung des angestrebten 1:2-Sandwichkomplexes aus Tetra-Zinkporphyrin-Perylenbisimid und Diazabicyclo-[2.2.2]-undecan wurde mittels UV/Vis und 1H NMR Spektroskopie untersucht und die makrocyclische Struktur des Komplexes konnte mittels diffusionsabh{\"a}ngiger NMR Spektroskopie (DOSY NMR) eindeutig bewiesen werden. Weiterhin konnte mittels rasterkraftmikroskopischer (AFM) Untersuchungen gezeigt werden, dass diese funktionellen makrocyclischen Verbindungen sehr geordnet auf einer Graphitoberfl{\"a}che (HOPG) abgeschieden werden k{\"o}nnen. Die Ausrichtung eines amino-funktionalsierten p-konjugierten Polymers durch Zugabe des bichromphoren Tetra-Zinkporphyrin-Perlyenbisimids wurde mittels UV/Vis-Spektroskopie und AFM-Messungen untersucht. Die Oberfl{\"a}chenanalyse mittels AFM zeigte, dass die bichromophore Verbindung die linearen p-konjugierten Polymere {\"u}ber weite Teile der Oberfl{\"a}che auszurichten vermag, so dass eine definierte Anordnung von drei p-Systemen auf der Graphitoberfl{\"a}che erm{\"o}glicht wurde.}, language = {en} } @phdthesis{Schmidt2008, author = {Schmidt, R{\"u}diger}, title = {Perylene Bisimide and Acene Derivatives as Organic Semiconductors in OTFTs}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-29314}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2008}, abstract = {This thesis deals with the synthesis of improved organic semiconductors, the detailed investigation of the molecular properties and the solid state arrangements revealed by single crystal X-ray diffraction and finally the development of structureperformance dependencies by measuring of the charge carrier mobilities of the derivatives in thin film transistors. The two main-goals of this thesis were achieved. Well soluble acene derivatives for spin-coated TFTs were obtained, showing charge carrier mobilities in the range of polymer p-type materials. Novel core-fluorinated perylene bisimide dyes were synthesized particularly and the use of electron deficient substituents lead to PBIs with outstanding air-stable mobilities in thin film transistors prepared by vacuum deposition techniques. The relationship between performance, air stability and solid state packing was elucidated in detail by single crystal X-ray diffraction analysis.}, subject = {D{\"u}nnschichttransistor}, language = {en} } @phdthesis{Hecht2021, author = {Hecht, Markus}, title = {Liquid-Crystalline Perylene Bisimide and Diketopyrrolopyrrole Assemblies}, doi = {10.25972/OPUS-21698}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-216987}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2021}, abstract = {The research presented in this thesis illustrates that self-assembly of organic molecules guided by intermolecular forces is a versatile bottom-up approach towards functional materials. Through the specific design of the monomers, supramolecular architectures with distinct spatial arrangement of the individual building blocks can be realized. Particularly intriguing materials can be achieved when applying the supramolecular approach to molecules forming liquid-crystalline phases as these arrange in ordered, yet mobile structures. Therefore, they exhibit anisotropic properties on a macroscopic level. It is pivotal to precisely control the interchromophoric arrangement as functions originate in the complex structures that are formed upon self-assembly. Consequently, the aim of this thesis was the synthesis and characterization of liquid-crystalline phases with defined supramolecular arrangements as well as the investigation of the structure-property relationship. For this purpose, perylene bisimide and diketopyrrolopyrrole chromophores were used as they constitute ideal building blocks towards functional supramolecular materials due to their thermal stability, lightfastness, as well as excellent optical and electronic features desirable for the application in, e.g., organic electronics.}, subject = {Selbstorganisation}, language = {en} } @phdthesis{Kaiser2009, author = {Kaiser, Theo E.}, title = {J-Aggregates of Tetraphenoxy-Substituted Perylene Bisimide Dyes}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-43544}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2009}, abstract = {In dieser Doktorarbeit wurde gezeigt, dass die sehr begehrte J-Aggregation funktionaler Perylenbisimid-Chromophore durch geeignetes Design der monomeren Bausteine erreicht werden kann. Hierzu war einerseits die Selbstanordnung durch ein Zusammenwirken von Wasserstoffbr{\"u}cken und Pi-Pi-Wechselwirkungen zu beg{\"u}nstigen, und andererseits eine Anordnung in kolumnaren Stapeln zu verhindern, was durch Kern-Verdrillung mittels sterisch anspruchsvollen Substituenten gelang. Desweiteren gaben Selbstanordnungsstudien neue Einblicke in den dynamischen Aggregationsprozess niedrigdimensionaler langgestreckter Aggregate mit stark exzitonisch gekoppelten Chromophoren. Die Beziehung zwischen bekannten Cyaninfarbstoffen, wie der von THIATS mit dem vorliegenden PBI 1a wurde durch Absorptions- und Fluoreszenzspektroskopie bei Tieftemperaturen von 5 K bis Raumtemperatur untersucht. Die vormals beispiellosen funktionalen Eigenschaften der PBI-Aggregate, welche aus der J-artigen exzitonischen Kopplung herr{\"u}hren, sind vielversprechend f{\"u}r die Anwendung in optoelektronischen Bauteilen und f{\"u}r die Photovoltaik.}, subject = {Perylenbisdicarboximide