1703
2006
eng
doctoralthesis
1
2006-10-27
--
2006-10-06
pi-Stacks Based on Self-Assembled Perylene Bisimides : Structural, Optical, and Electronic Properties
pi-Stapel von selbstaggregierten Perylenbisimiden : Strukturelle, Optische und Electronische Eigenschaften
As a traditional industrial pigment, perylene bisimide (PBI) dyes have found wide-spread applications. In addition, PBI dyes have been considered as versatile and promising functional materials for organic-based electronic and optic devices, such as transistors and solar cells. For these novel demands, the control of self-organization of this type of dye and the investigation of the relationship between the supramolecular structure and the relevant optical and electronic properties is of great importance. The objective of this thesis focuses on gaining a better understanding of structural and functional properties of pi-stacks based on self-assembling PBIs. Studies include the synthesis and characterization of new functional PBI dyes, their aggregation in solution, in liquid crystalline state and on surfaces, and their fluorescence and charge transport properties. An overview of the formation, thermodynamics and structures of pi-stacks of functional pi- conjugated molecules in solution and in liquid crystalline phases is given in Chapter 2. Chapters 3 and 4 deal with the pi-pi aggregates of new, highly fluorescent PBIs without core-substituents. In Chapter 3, the self-assembly of a PBI with tridodecylphenyl substituents at imide N atoms both in solution and condensed phase has been studied in great detail. In condensed state, the dye exhibits a hexagonal columnar liquid crystalline (LC) phase as confirmed by DSC, OPM and X-ray diffraction analysis. The columnar stacking of this dye has been further confirmed by atomic force microscopy (AFM) where single columns could be well resolved The charge transport properties this dye have been investigated by pulse radiolysis-time resolved microwave conductivity (PR-TRMC) measurements. To shed more light on the nature of the pi-pi interaction of the unsubstituted PBIs, solvent depend aggregation properties have been investigated in Chapter 4. The studies are further extended from core-unsubstituted PBIs to core-substituted ones (Chapter 5 and 6). In Chapter 5, a series of highly soluble and fluorescent core-twisted PBIs that bear the same trialkylphenyl groups at the imide positions but different bay-substituents and were synthesized. These compounds are characterized by distortions of the perylene planes with dihedral angles in the range of 15-37° according to crystallographic data and molecular modeling studies. In contrast to the extended oligomeric aggregates formed for planar unsubstituted PBIs, this family of dyes formed discrete pi-pi-stacked dimers in apolar methylcyclohexane as concentration-dependent UV/Vis measurements and VPO analysis revealed. The Gibbs free energy of dimerization can be correlated with the twist angles of the dyes linearly. In condensed state, several of these PBIs form luminescent rectangular or hexagonal columnar liquid crystalline phases with low isotropization temperatures. The core-twisting effect on semiconducting properties has been examined in Chapter 6. In this chapter, a comparative study of the electrochemical and the charge transport properties of a series of non-substituted and chlorine-functionalized PBIs was performed. While Chapters 3-6 focus on one-component dye systems, Chapter 7 explored the possibility of a supramolecular engineering of co-aggregates formed by hydrogen-bonded 2:1 and 1:1 complex of oligo(p-phenylene vinylene)s (OPVs) and PBIs. Covalently linked donor-acceptor dye arrays have been prepared for comparison. Concentration and temperature-dependent UV/Vis spectroscopy revealed all hydrogen-bonded and covalent systems form well-ordered J-type aggregates in methylcyclohexane. With these hydrogen-bonded OPV-PBI complexes, fibers containing p-type and n-type molecules can be prepared on the nano-scale (1-20 nm). For the 2:1 OPV-PBI hydrogenbonded arrays hierarchically assembled chiral superstructures consisting of left-handed helical pi-pi co-aggregates (CD spectroscopy) of the two dyes that further assemble into right-handed nanometer-scale supercoils in the solid state (AFM study) have been observed. All of these well-defined OPV-PBI assemblies presented here exhibit photoinduced electron transfer on sub-ps timescale, while the electron recombination differs for different systems.Thus, it was suggested that such assemblies of p- and n-type semiconductors might serve as valuable nanoscopic functional units for organic electronics.
Als traditionsreiches in industriellem Maßstab produziertes Pigment finden Perylenbisimid (PBI)-Farbstoffe Verwendung in vielen verschiedenen Anwendungsgebieten. Außerdem sind diese Farbstoffe aufgrund ihrer vielseitigen funktionellen Eigenschaften aussichtsreiche Kandidaten für auf organischen Materialen basierende elektronische und optische Einheiten, wie z.B. Transistoren oder Solarzellen. Für diese neuen Herausforderungen ist die gezielte Kontrolle bzw. Steuerung der Selbstorganisation dieser Farbstofftypen sowie die Erforschung des Zusammenhangs zwischen der supramolekularen Struktur und den optischen und elektronischen Eigenschaften von großem Interesse. Ziel dieser Arbeit war es daher, ein besseres Verständnis für strukturelle und funktionelle Eigenschaften pi-gestapelter Chromophore am Beispiel selbst-aggregierender PBI-Farbstoffe zu entwickeln. Dies umfaßt die Synthese und die Charakterisierung neuer funktioneller PBI-Farbstoffe, die Untersuchung ihrer Aggregate in Lösung, in flüssigkristallinen Phasen, Dünnschichten auf verschiedenen Oberflächen, sowie der Fluoreszenz- und Ladungsträgertransporteigenschaften. Ein Überblick über den Selbstaggregationsprozess, die thermodynamischen Eigenschaften und die Strukturen von pi-Stapeln verschiedener funktioneller pi-konjugierter Moleküle in Lösung und in flüssigkristallinen Phasen wird in Kapitel 2 gegeben. Kapitel 3 und 4 beschäftigen sich mit den pi-pi-Aggregaten neuartiger, stark fluoreszierender PBIs ohne Kernsubstituenten. In Kapitel 3 wurde das Aggregationsverhalten eines PBIs mit Tridodecylphenyl-Substituenten an den Imid-N-Atomen sowohl in Lösung als auch in der kondensierten Phase sehr detailiert untersucht. In der kondensierten Phase wurde eine kolumnar-hexagonale flüssigkristalline (LC) Phase mittels Differenzialkalorimetrie (DSC), optischer Polarisationsmikroskopie und Pulverröntgendiffraktometrie nachgewiesen. Die eindimensionale Stapelanordnung wurde zudem mittels Rasterkraftmikroskopie (AFM) bestätigt, welche ausgedehnte kolumnare Strukturen ergaben. Die Ladungstransporteigenschaften dieses Farbstoffes wurden mittels „pulse radiolysis-time resolved microwave“ (PR-TRMC) Experimenten untersucht. Zur weiteren Aufklärung der Natur der pi-pi-Interaktion des unsubstituierten PBI wurden in Kapitel 4 die lösungsmittelabhängigen Eigenschaften untersucht. Die Studien wurden zudem ausgedehnt von kernunsubstituierten auf kernsubstituierte PBIFarbstoffe. In Kapitel 5 werden die Synthesen einer Reihe sehr gut löslicher, fluoreszierender, nichtplanarer PBI-Farbstoffe vorgestellt, welche dieselben Trialkylphenylimidisubstituenten, jedoch unterschiedliche Bay-Substituenten tragen. Für diese Substanzen wurden mittels kristallographischer Daten sowie quantenchemischer Berechnungen Diederwinkelwinkel im Bereich 15 bis 37° ermittelt. Im Gegensatz zu den ausgedehnten oligomeren Aggregaten des planaren PBI bildet diese Farbstoffklasse aufgrund der Verdrillung des aromatischen Kerns in apolaren Lösungsmitteln wie Methylcyclohexan diskrete pi-pi-gestapelte Dimere. Die Freie Enthalpie für die Dimerisierung korreliert dabei linear mit dem Verdrillungswinkel. In der kondensierten Phase bilden einige dieser PBI-Farbstoffe fluoreszierende, rektangulare bzw. hexagonale kolumnare LC Phasen mit niedrigen Klärtemperaturen. In Kapitel 6 wurden die Auswirkungen des Verdrillungswinkels auf die Halbleitereigenschaften untersucht. Es wurden vergleichende Studien der elektrochemischen Eigenschaften sowie der Ladungsträgertransporteigenschaften einer Serie unsubstituierter und chlorfunktionalisierter PBI-Farbstoffe durchgeführt. Während in Kapitel 3-6 der Fokus auf Einkomponenten-Farbstoffaggregaten lag, wurde in Kapitel 7 die Möglichkeiten einer supramolekularer Anordnung von Co-Aggregaten untersucht, welche durch wasserstoffbrückengebundene 2:1 und 1:1 Komplexe zwischen Oligo(p-phenylenevinylenen) (OPVs) und PBIs aufgebaut sind. Mit diesen wasserstoffbrückengebundenen OPV-PBI Komplexen lassen sich eindimensionale Aggregate auf der Nanoskala erzeugen, welche aus p- und n-halbleitenden Molekülen bestehen. Für die wasserstoffbrückengebundenen 2:1 OPV-PBI Komplexe wurden Anordnungen beobachtet, welche chirale Überstrukturen mit links-drehenden, helicalen pi-pi- Co-Aggregaten (CD-Spectroscopie) aufweisen, die sich wiederum in rechts-drehenden Superhelices bündeln (AFM-Studien). Während für alle OPV-PBI Aggregate photoinduzierte Elektronentransferprozesse im subps Zeitskalenbereich beobachtet wurden, unterschieden sich die Rekombinationsraten je nach System beträchtlich. Somit ist diese Art von organisierten nanoskopischen p- und n-halbleitenden funktionellen. Bausteinen aussichtsreich für verschiedene Anwendungen in der Organischen Elektronik.
urn:nbn:de:bvb:20-opus-19940
1994
X120987
Zhijian Chen
deu
swd
Perylenderivate
deu
swd
Farbstoff
deu
swd
Flüssigkristall
deu
swd
Selbstorganisation
deu
uncontrolled
Perylenbisimiden
deu
uncontrolled
selbstaggregierten
deu
uncontrolled
Flüssigkristall
deu
uncontrolled
Farbstoff
eng
uncontrolled
perylene bisimide
eng
uncontrolled
self-assembly
eng
uncontrolled
liquid crystal
eng
uncontrolled
functional dyes
Chemie und zugeordnete Wissenschaften
open_access
Institut für Organische Chemie
Universität Würzburg
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/1703/thesis-Chen-2006.pdf
20471
2018
eng
6904-6911
9
article
1
2020-05-26
--
--
Hydrogen-bonded perylene bisimide J-aggregate aqua material
A new twelvefold methoxy-triethyleneglycol-jacketed tetraphenoxy-perylene bisimide (MEG-PBI) amphiphile was synthesized that self-assembles into two types of supramolecular aggregates in water: red-coloured aggregates of low order and with weak exciton coupling among the PBIs and blue-coloured strongly coupled J-aggregates consisting of a highly ordered hydrogen-bonded triple helix of PBIs. At room temperature this PBI is miscible with water at any proportions which enables the development of robust dye aggregates in solution, in hydrogel states and in lyotropic liquid crystalline states. In the presence of 60–95 wt% water, self-standing coloured hydrogels exhibit colour changes from red to blue accompanied by a fluorescence light-up in the far-red region upon heating in the range of 30–50 °C. This phenomenon is triggered by an entropically driven temperature-induced hydrogen-bond-directed slipped stacking arrangement of the MEG-PBI chromophores within structurally well-defined J-aggregates. This versatile aqua material is the first example of a stable PBI J-aggregate in water. We anticipate that this study will open a new avenue for the development of biocompatible functional materials based on self-assembled dyes and inspire the construction of other hydrogen-bonded supramolecular materials in the highly competitive solvent water.
10.1039/C8SC02409J
https://doi.org/10.1039/C8SC02409J
2041-6539
urn:nbn:de:bvb:20-opus-204715
Chemical Science, 2018, 9, 6904–6911. DOI: 10.1039/c8sc02409j
643238
Vincenzo Grande
Bartolome Soberats
Stefanie Herbst
Vladimir Stepanenko
Frank Würthner
eng
uncontrolled
self-assembly
eng
uncontrolled
dyes
eng
uncontrolled
aqua material
Organische Chemie
open_access
Institut für Organische Chemie
OpenAIRE
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/20471/Wuerthner_ChemicalScience_2018.pdf
22458
2020
eng
17084
17090
39
59
article
1
--
--
--
Self‐Sorting Supramolecular Polymerization: Helical and Lamellar Aggregates of Tetra‐Bay‐Acyloxy Perylene Bisimide
A new perylene bisimide (PBI), with a fluorescence quantum yield up to unity, self‐assembles into two polymorphic supramolecular polymers. This PBI bears four solubilizing acyloxy substituents at the bay positions and is unsubstituted at the imide position, thereby allowing hydrogen‐bond‐directed self‐assembly in nonpolar solvents. The formation of the polymorphs is controlled by the cooling rate of hot monomer solutions. They show distinctive absorption profiles and morphologies and can be isolated in different polymorphic liquid‐crystalline states. The interchromophoric arrangement causing the spectral features was elucidated, revealing the formation of columnar and lamellar phases, which are formed by either homo‐ or heterochiral self‐assembly, respectively, of the atropoenantiomeric PBIs. Kinetic studies reveal a narcissistic self‐sorting process upon fast cooling, and that the transformation into the heterochiral (racemic) sheetlike self‐assemblies proceeds by dissociation via the monomeric state.
Angewandte Chemie International Edition
10.1002/anie.202006744
urn:nbn:de:bvb:20-opus-224586
2021-02-15T14:01:00+00:00
sword
swordwue
attachment; filename=deposit.zip
bd5a8a0761cb6913b980dc9101d96a11
Angewandte Chemie International Edition 2020, 59(39):17084–17090. DOI: 10.1002/anie.202006744
false
true
CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International
Markus Hecht
Pawaret Leowanawat
Tabea Gerlach
Vladimir Stepanenko
Matthias Stolte
Matthias Lehmann
Frank Würthner
eng
uncontrolled
liquid crystals
eng
uncontrolled
noncovalent interactions
eng
uncontrolled
self-assembly
eng
uncontrolled
structure elucidation
eng
uncontrolled
supramolecular chemistry
Chemie und zugeordnete Wissenschaften
open_access
Institut für Organische Chemie
Import
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/22458/ANIE_ANIE202006744.pdf
3534
2009
eng
doctoralthesis
1
2010-01-04
--
2009-12-23
Hydrogen Bond-directed Self-assembly of Perylene Bisimide Organogelators
Perylene bisimide (PBI) dyes are a widely used class of industrial pigments, and currently have gained significant importance for organic-based electronic and optical devices. Structural modification at the PBI core results in changes of the optical and electronic properties, which enable tailored functions. Moreover, the aggregation behavior of PBIs is alterable and controllable to achieve new materials, among which organogels are of particular interest because of their potential for applications as supramolecular soft materials. In this work, new PBI-based organic gelators were designed, synthesized, and characterized, and the aggregation behaviors under different conditions were intensively studied by various spectroscopic and microscopic methods. In chapter 2, a brief overview is given on the structural and functional features of organogel systems. The definition, formation and reversibility of organogels are introduced. Some examples on dye based organogel are selected, among which PBI-based organogelators reported so far are especially emphasized. Some basic knowledges of supramolecular chirality are also overviewed such as characterization, amplification, and symmetry breaking of the chiral aggregates. According to our former experiences, PBIs tend to form aggregates because the planer aromatic cores interact with one another by pi-pi interaction. In chapter 3, a new PBI molecule is introduced which possesses amide groups between the conjugated core and periphery alkyl chains. It is found that well oriented aggregates are formed by hydrogen bonding and the pi-pi interaction of the cores. These interactions enable the aggregates to grow in one-dimension forming very long fibers, and these fibers further intercross to 3D network structures, e.g., organogels. In comparison to the very few PBI-based gelators reported before, one advantage of this gelator is that, it is more versatile and can gelate a wide range of organic solvents. Moreover, the well-organized fibers that are composed of extended π-stacks provide efficient pathways for n-type charge carriers. Interestingly, AFM studies reveal that the PBI molecules form well-defined helical fibers in toluene. Both left-handed (M) and right-handed (P) helicities can be observed without any preference for one handedness because the building block is intrinsically achiral. In chapter 4, we tried to influence the M/P enantiomeric ratio by applying external forces. For example, we utilized chiral solvents to generate chiral aggregates with a preferential handedness. AFM analysis of the helices showed that a enantiomeric ratio of about 60: 40 can be achieved by aggregation in chiral solvents R- or S-limonene. Moreover, the long aggregated fibres can align at macroscopic level in vortex flows upon rotary stirring In chapter 5, bulky tetra-phenoxy groups are introduced in the bay area of the PBI gelator. The conjugated core of the new molecule is now distorted because of the steric hindrance. UV/Vis studies reveal a J-type aggregation in apolar solvents like MCH due to intermolecular pi-pi-stacking and hydrogen-bonding interactions. Microscopic studies reveal formation of columnar aggregates in apolar solvent MCH, thus this molecule lacks the ability to form gels in this solvent, but form highly fluorescent lyotropic mesophases at higher concentration. On the other hand, in polar solvents like acetone and dioxane, participation of the solvent molecules in hydrogen bonding significantly reduced the aggregation propensity but enforced the gel formation. The outstanding fluorescence properties of the dye in both J-aggregated viscous lyotropic mesophases and bulk gel phases suggest very promising applications in photonics, photovoltaics, security printing, or as fluorescent sensors. In chapter 6, we did some studies on combining PBI molecules with inorganic gold nanorods. Gold nanorods were synthesized photochemically. By virtue of the thioacetate functionalized PBIs, the rods were connected end to end to form gold nanochains, which were characterized by absorption spectra and TEM measurement. Such chromophore-nanorod hybrids might be applied to guide electromagnetic radiation based on optical antenna technology.
urn:nbn:de:bvb:20-opus-43727
4372
X122750
Xueqing Li
deu
swd
Perylenderivate
deu
swd
Selbstorganisation
deu
swd
Wasserstoffbrückenbindung
deu
swd
Gelieren
deu
swd
Supramolekulare Struktur
eng
uncontrolled
organogelator
eng
uncontrolled
perylene bisimide
eng
uncontrolled
self-assembly
Naturwissenschaften und Mathematik
open_access
Institut für Organische Chemie
Universität Würzburg
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/3534/PhD_Thesis_Xueqing_Li.pdf
34610
2023
eng
doctoralthesis
1
2023-12-08
--
2023-12-07
Twisted Rylene Bisimides for Organic Solar Cells and Strong Chiroptical Response in the Near Infrared
Kernverdrillte Rylenbisimide für organische Solarzellen und starke chirooptische Eigenschaften im Nahinfrarot
The chirality of the interlocked bay-arylated perylene motif is investigated upon its material prospect and the enhancement of its chiroptical response to the NIR spectral region. A considerable molecular library of inherently chiral perylene bisimides (PBIs) was utilized as acceptors in organic solar cells to provide decent device performances and insights into the structure-property relationship of PBI materials within a polymer blend. For the first time in the family of core-twisted PBIs, the effects of enantiopurity on the device performance was thoroughly investigated. The extraordinary structural sensitivity of CD spectroscopy served as crucial analytical tool to bridge the highly challenging gap between molecular properties and device analytics by proving the excitonic chirality of a helical PBI dimer. The chirality of this perylene motif could be further enhanced on a molecular level by both the expansion and the enhanced twisting of the π-scaffold to achieve a desirable strong chiroptical NIR response introducing a new family of twisted QBI-based nanoribbons. These achievements could be substantially further developed by expanding this molecular concept to a supramolecular level. The geometrically demanding supramolecular arrangement necessary for the efficient excitonic coupling was carefully encoded into the molecular design. Accordingly, the QBIs could form the first J-type aggregate constituting a fourfold-stranded superhelix of a rylene bisimide with strong excitonic chirality. Therefore, this thesis has highlighted the mutual corroboration of experimental and theoretical data from the molecular to the supramolecular level. It has demonstrated that for rylene bisimide dyes, the excitonic contribution to the overall chiroptical response can be designed and rationalized. This can help to pave the way for new organic functional materials to be used for
chiral sensing or chiral organic light-emitting devices.
Die Chiralität des verzahnten Bucht-arylierten Perylenmotivs wurde im Hinblick auf seine Materialanwendung sowie die Verstärkung seiner chiroptischen Eigenschaften im NIR-Spektralbereich untersucht. Eine umfangreiche Molekülbibliothek von inhärent chiralen PBIs wurde als NFAs in OSCs verwendet, um sowohl gute Solarzelleneffizienzen sowie Einblicke in die Struktur-Eigenschafts-Beziehung von PBI Materialien innerhalb einer Polymermischung zu erhalten. Zum ersten Mal wurden für kernverdrillte PBIs die Auswirkungen der Enantiomerenreinheit auf die Effizienz von organischen Dünnfilmbauteilen untersucht. Die außerordentliche strukturelle Empfindlichkeit der CD Spektroskopie diente als entscheidendes Analysewerkzeug, um die hoch anspruchsvolle Lücke zwischen der Analytik molekularer Eigenschaften und der Bauteilanalytik zu schließen, indem die exzitonische Chiralität eines helikalen PBI-Dimers nachgewiesen wurde. Die Chiralität dieses Perylenmotivs konnte auf molekularer Ebene weiter verstärkt werden, indem das π-Gerüst sowohl erweitert als auch stärker verdrillt wurde, um wünschenswert starke chiroptische Eigenschaften im NIR-Bereich zu erzielen und so eine neue Molekülfamilie kernverdrillter QBIs zu definieren. Diese Errungenschaften konnten durch die Ausweitung dieses molekularen Konzepts auf eine supramolekulare Ebene noch erheblich weiterentwickelt werden. Die geometrisch anspruchsvolle supramolekulare Anordnung, die für die effiziente exzitonische Kopplung erforderlich ist, wurde sorgfältig in das molekulare Design kodiert. Dementsprechend stellt das präsentierte QBI in seiner vierfach versetzt gestapelten Superhelix das erste Rylenbisimid-J-Aggregat dar, welches eine starke exzitonische Chiralität zeigt.
Somit hat die Arbeit hat die gegenseitige Bestätigung von experimentellen und theoretischen Daten von der molekularen bis hin zur supramolekularen Ebene herausgestellt und gezeigt, dass für Rylenbisimid-Farbstoffe der exzitonische Beitrag zu den chiroptischen Eigenschaften konzipiert, synthetisch realisiert und quantenmechanisch verstanden werden kann. Dies kann den Weg für neue organische Funktionsmaterialien ebnen, die für chirale Sensoren oder Licht emittierende Bauteile verwendet werden können.
urn:nbn:de:bvb:20-opus-346106
10.25972/OPUS-34610
publish
X 130825
CC BY-SA: Creative-Commons-Lizenz: Namensnennung, Weitergabe unter gleichen Bedingungen 4.0 International
Bernhard Mahlmeister
deu
swd
Molekül
deu
swd
Chiralität <Chemie>
deu
swd
Exziton
deu
swd
Organische Solarzelle
deu
swd
Supramolekulare Chemie
eng
uncontrolled
organic solar cell
eng
uncontrolled
non-fullerene acceptor
eng
uncontrolled
perylene bisimide
eng
uncontrolled
quaterrylene bisimide
eng
uncontrolled
inherent chirality
eng
uncontrolled
excitonic chirality
eng
uncontrolled
supramolecular chemistry
eng
uncontrolled
self-assembly
eng
uncontrolled
near infrared chirality
Organische Chemie
open_access
Institut für Organische Chemie
Universität Würzburg
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/34610/Mahlmeister_Bernhard_Dissertation.pdf
31209
2023
eng
2
7
article
1
--
--
--
Supramolecularly Engineered Bulk‐Heterojunction Solar Cells with Self‐Assembled Non‐Fullerene Nanographene Tetraimide Acceptors
A series of novel imide‐functionalized C\(_{64}\) nanographenes is investigated as acceptor components in organic solar cells (OSCs) in combination with donor polymer PM6. These electron‐poor molecules either prevail as a monomer or self‐assemble into dimers in the OSC active layer depending on the chosen imide substituents. This allows for the controlled stacking of electron‐poor and electron‐rich π–scaffolds to establish a novel class of non‐fullerene acceptor materials to tailor the bulk‐heterojunction morphology of the OSCs. The best performance is observed for derivatives that are able to self‐assemble into dimers, reaching power conversion efficiencies of up to 7.1%.
Solar RRL
10.1002/solr.202200895
urn:nbn:de:bvb:20-opus-312099
2023-04-19T16:28:02+00:00
sword
swordwue
attachment; filename=deposit.zip
e0e3b16d0e54ecdb377e55b97bdcbdb8
Solar RRL 2023, 7(2):2200895. DOI: 10.1002/solr.202200895
false
true
CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International
Kaan Menekse
Magnus Mahl
Julius Albert
M. A. Niyas
Kazutaka Shoyama
Matthias Stolte
Frank Würthner
eng
uncontrolled
nanographene
eng
uncontrolled
non-fullerene acceptors
eng
uncontrolled
organic solar cells
eng
uncontrolled
polycyclic aromatic hydrocarbons
eng
uncontrolled
self-assembly
Chemie und zugeordnete Wissenschaften
open_access
Institut für Organische Chemie
Import
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/31209/Meneske_Solar.pdf
20465
2020
eng
article
1
2020-05-25
--
--
Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation
Herein we report a broad series of new trinuclear supramolecular Ru(bda) macrocycles bearing different substituents at the axial or equatorial ligands which enabled investigation of substituent effects on the catalytic activities in chemical and photocatalytic water oxidation. Our detailed investigations revealed that the activities of these functionalized macrocycles in water oxidation are significantly affected by the position at which the substituents were introduced. Interestingly, this effect could not be explained based on the redox properties of the catalysts since these are not markedly influenced by the functionalization of the ligands. Instead, detailed investigations by X-ray crystal structure analysis and theoretical simulations showed that conformational changes imparted by the substituents are responsible for the variation of catalytic activities of the Ru macrocycles. For the first time, macrocyclic structure of this class of water oxidation catalysts is unequivocally confirmed and experimental indication for a hydrogen-bonded water network present in the cavity of the macrocycles is provided by crystal structure analysis. We ascribe the high catalytic efficiency of our Ru(bda) macrocycles to cooperative proton abstractions facilitated by such a network of preorganized water molecules in their cavity, which is reminiscent of catalytic activities of enzymes at active sites.
10.1039/d0sc01097a
https://doi.org/10.1039/D0SC01097A
2041-6539
urn:nbn:de:bvb:20-opus-204653
787937
Chemical Science, 2020, Advance Articl. https://doi.org/10.1039/D0SC01097A
false
true
Ana-Lucia Meza-Chincha
Joachim O. Lindner
Dorothee Schindler
David Schmidt
Ana-Maria Krause
Merle I. S. Röhr
Roland Mitrić
Frank Würthner
eng
uncontrolled
water oxidation
eng
uncontrolled
self-assembly
eng
uncontrolled
solar fuels
eng
uncontrolled
supramolecular materials
eng
uncontrolled
catalysis
Organische Chemie
open_access
Institut für Organische Chemie
Institut für Physikalische und Theoretische Chemie
OpenAIRE
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/20465/Wuerthner_ChemicalScience_2020.pdf
2430
2008
eng
doctoralthesis
1
2008-08-04
--
2008-07-25
A Guide to Supramolecular Assemblies in Polar Solutions - From Nanometre-Sized Cyclic Dimers to Large Vesicular Structures
Ein Leitfaden für supramolekulare Verbände in polaren Lösungen - Von Nanometer-großen zyklischen Dimeren zu großen vesikularen Strukturen
This PhD thesis introduced several concepts for the construction of new supramolecular assem-blies in polar solvents. Although the building blocks differ in their binding mode and association strength they follow the same principle: one main driving force for the self-assembly in polar solutions in combination with one texturing force. The main self-assembly process is based on the mutual interaction of hydrogen-bond enforced ion pairs which deliver the association energy needed for stable, supramolecular structures even in polar solvents. The texturing force itself is represented by the linkers between the zwitterionic building blocks or parts of them. The different length and functionalization of the linkers have a tremendous influence on the mode of self-assembly leading to cyclic dimers, vesicles, layers or solid spheres. Hence, this principle is suitable for the construction of programmable monomers. Since the derivatisation of the main binding motive is rather simple it offers a great number of new and undoubtedly fascinating structures with potential applications in material and biomimetic science.
Diese Doktorarbeit stellte mehrere Konzept für den Aufbau von neuen supramolekularen Verbindungen in polaren Solventien vor. Obwohl sich die Bausteine bezüglich ihres Bindungsmodus und ihrer Assoziationsstärke unterscheiden, folgen sie alle dem gleichen Prinzip: eine Haupttriebkraft für den Selbstassoziationsprozess in polaren Lösemitteln in Kombination mit einer strukturgebenden Kraft. Die Haupttriebkraft stellen wasserstoffbrückenbindungsvermittelte Ionenpaare dar, die die nötige Assoziationsenergie für stabile, supramolekulare Strukturen auch in polaren Lösungen liefern. Die strukturierende Kraft selbst wird durch die Linkermoleküle zwi-schen den Zwitterionen oder Teilen von diesen vermittelt. Die unterschiedliche Länge und Funktionalisierung der Linker haben einen enormen Einfluss auf den Modus der Selbstassoziation, so dass die Bildung von zyklischen Dimeren, Vesikeln, Schichten oder Vollkugeln möglich war. Daher kann dieses Konzept für den Aufbau von programmierbaren Monomeren verwendet werden. Die Derivatisierung des zwitterionischen Bindungsmotivs gestaltet sich relativ einfach, so dass eine große Anzahl von neuen und zweifelsohne faszinierenden Nanostrukturen für zukünftige Anwendungen in der Materialwissenschaft und Biomimetik zur Verfügung steht.
urn:nbn:de:bvb:20-opus-28359
2835
X121991
Thomas Helge Rehm
deu
swd
Supramolekulare Chemie
deu
uncontrolled
Vesikel
deu
uncontrolled
Selbstassoziation
deu
uncontrolled
polare Lösung
eng
uncontrolled
vesicle
eng
uncontrolled
self-assembly
eng
uncontrolled
polar solution
Chemie und zugeordnete Wissenschaften
open_access
Institut für Organische Chemie
Universität Würzburg
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/2430/RehmDiss.pdf
13324
2015
eng
doctoralthesis
1
2016-05-09
--
2016-04-22
Self-assembly of amphiphilic oligo(phenylene ethynylene)-based (bi)pyridine ligands and their Pt(II) and Pd(II) complexes
Selbstorganisation von amphiphilen oligo(phenylenethinylen)-basierten (Bi)pyridin-Liganden und ihrer Pt(II) und Pd(II) Komplexe
The presented work in the field of supramolecular chemistry describes the synthesis and detailed investigation of (bi)pyridine-based oligo(phenylene ethynylene) (OPE) amphiphiles, decorated with terminal glycol chains. The metal-ligating property of these molecules could be exploited to coordinate to Pd(II) and Pt(II) metal ions, respectively, resulting in the creation of novel metallosupramolecular π-amphiphiles of square-planar geometry.
The focus of the presented studies is on the self-assembly behaviour of the OPE ligands and their corresponding metal complexes in polar and aqueous environment. In this way, the underlying aggregation mechanism (isodesmic or cooperative) is revealed and the influence of various factors on the self-assembly process in supramolecular systems is elucidated. In this regard, the effect of the molecular design of the ligand, the coordination to a metal centre as well as the surrounding medium, the pH value and temperature is investigated.
Die vorliegende Arbeit auf dem Gebiet der Supramolekularen Chemie beschäftigt sich mit der Synthese und detaillierten Untersuchung von (bi)pyridin-basierten Oligo(phenylenethinylen) (OPE)-Amphiphilen mit endständigen Glykolketten. Die komplexierende Eigenschaft dieser Moleküle wurde ausgenutzt um sie an Pd(II) bzw. Pt(II) Metallionen zu koordinieren, wobei neuartige metallosupramolekulare π-Amphiphile von quadratisch-planarer Geometrie entstehen.
Das Hauptaugenmerk der beschriebenen Studien liegt auf der Selbstorganisation der OPE-Liganden und ihrer Metallkomplexe in polarer und wässriger Umgebung. Dabei wurde der zu Grunde liegende Aggregationsmechanismus (isodesmisch oder kooperativ) bestimmt und der Einfluss verschiedener Faktoren auf den Selbstorganisationsprozess in supramolekularen Systemen aufzeigt. Neben dem Effekt des Moleküldesigns des Liganden und dessen Koordination an ein Metallzentrum wird auch der des umgebenden Mediums, des pH-Wertes sowie der Temperatur erläutert.
urn:nbn:de:bvb:20-opus-133248
X 126525
Deutsches Urheberrecht
Christina Rest
deu
swd
Supramolekulare Chemie
deu
swd
Selbstorganisation
deu
swd
Kooperativität
deu
swd
Aggregat <Chemie>
deu
swd
Amphiphile Verbindungen
eng
uncontrolled
cooperativity
eng
uncontrolled
non-covalent interactions
eng
uncontrolled
(bi)pyridine-based ligand
eng
uncontrolled
oligo(phenylene ethynylene) (OPE)
eng
uncontrolled
self-assembly
eng
uncontrolled
metallosupramolecular π-amphiphiles
deu
uncontrolled
Aggregation
Chemie und zugeordnete Wissenschaften
open_access
Institut für Organische Chemie
Universität Würzburg
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/13324/Rest_Christina_DrArbeit.pdf
12943
2013
eng
1541-1565
1
14
article
1
2016-03-10
--
--
Aqueous Self-Sorting in Extended Supramolecular Aggregates
Self-organization and self-sorting processes are responsible for the regulation and control of the vast majority of biological processes that eventually sustain life on our planet. Attempts to unveil the complexity of these systems have been devoted to the investigation of the binding processes between artificial molecules, complexes or aggregates within multicomponent mixtures, which has facilitated the emergence of the field of self-sorting in the last decade. Since, artificial systems involving discrete supramolecular structures, extended supramolecular aggregates or gel-phase materials in organic solvents or—to a lesser extent—in water have been investigated. In this review, we have collected diverse strategies employed in recent years to construct extended supramolecular aggregates in water upon self-sorting of small synthetic molecules. We have made particular emphasis on co-assembly processes in binary mixtures leading to supramolecular structures of remarkable complexity and the influence of different external variables such as solvent and concentration to direct recognition or discrimination processes between these species. The comprehension of such recognition phenomena will be crucial for the organization and evolution of complex matter.
International Journal of Molecular Sciences
10.3390/ijms14011541
urn:nbn:de:bvb:20-opus-129435
International Journal of Molecular Sciences 2013, 14, 1541-1565; doi:10.3390/ijms14011541
Christina Rest
María José Mayoral
Gustavo Fernández
eng
uncontrolled
co-aggregation
eng
uncontrolled
self-sorting
eng
uncontrolled
supramolecular chemistry
eng
uncontrolled
self-assembly
Organische Chemie
open_access
Institut für Organische Chemie
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/12943/051_Rest_Mayoral_Fernandez.pdf