@article{GrandeSoberatsHerbstetal.2018, author = {Grande, Vincenzo and Soberats, Bartolome and Herbst, Stefanie and Stepanenko, Vladimir and W{\"u}rthner, Frank}, title = {Hydrogen-bonded perylene bisimide J-aggregate aqua material}, volume = {9}, issn = {2041-6539}, doi = {10.1039/C8SC02409J}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-204715}, pages = {6904-6911}, year = {2018}, abstract = {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.}, language = {en} } @article{GoerlSoberatsHerbstetal.2016, author = {G{\"o}rl, Daniel and Soberats, Bartolome and Herbst, Stefanie and Stepanenko, Vladimir and W{\"u}rthner, Frank}, title = {Perylene bisimide hydrogels and lyotropic liquid crystals with temperature-responsive color change}, series = {Chemical Science}, volume = {7}, journal = {Chemical Science}, number = {11}, doi = {10.1039/c6sc02249a}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-162459}, pages = {6786-6790}, year = {2016}, abstract = {The self-assembly of perylene bisimide (PBI) dyes bearing oligo ethylene glycol (OEG) units in water affords responsive functional nanostructures characterized by their lower critical solution temperature (LCST). Tuning of the LCST is realized by a supramolecular approach that relies on two structurally closely related PBI-OEG molecules. The two PBIs socially co-assemble in water and the resulting nanostructures exhibit a single LCST in between the transition temperatures of the aggregates formed by single components. This permits to precisely tune the transition from a hydrogel to a lyotropic liquid crystal state at temperatures between 26 and 51 °C by adjusting the molar fraction of the two PBIs. Owing to concomitant changes in PBI-PBI interactions this phase transition affords a pronounced color change with "fluorescence-on" response that can be utilized as a smart temperature sensory system.}, language = {en} } @article{PratiharGhoshStepanenkoetal.2010, author = {Pratihar, Pampa and Ghosh, Suhrit and Stepanenko, Vladimir and Patwardhan, Sameer and Grozema, Ferdinand C. and Siebbeles, Laurens D. A. and W{\"u}rthner, Frank}, title = {Self-assembly and semiconductivity of an oligothiophene supergelator}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-67817}, year = {2010}, abstract = {A bis(trialkoxybenzamide)-functionalized quaterthiophene derivative was synthesized and its self-assembly properties in solution were studied. In non-polar solvents such as cyclohexane, this quaterthiophene π-system formed fibril aggregates with an H-type molecular arrangement due to synergistic effect of hydrogen bonding and π-stacking. The self-assembled fibres were found to gelate numerous organic solvents of diverse polarity. The charge transport ability of such elongated fibres of quaterthiophene π-system was explored by the pulse radiolysis time resolved microwave conductivity (PR-TRMC) technique and moderate mobility values were obtained. Furthermore, initial AFM and UV-vis spectroscopic studies of a mixture of our electron-rich quaterthiophene derivative with the electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) revealed a nanoscale segregated assembly of the individual building blocks in the blend.}, subject = {Organische Chemie}, 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} } @article{HechtLeowanawatGerlachetal.2020, author = {Hecht, Markus and Leowanawat, Pawaret and Gerlach, Tabea and Stepanenko, Vladimir and Stolte, Matthias and Lehmann, Matthias and W{\"u}rthner, Frank}, title = {Self-Sorting Supramolecular Polymerization: Helical and Lamellar Aggregates of Tetra-Bay-Acyloxy Perylene Bisimide}, series = {Angewandte Chemie International Edition}, volume = {59}, journal = {Angewandte Chemie International Edition}, number = {39}, doi = {10.1002/anie.202006744}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-224586}, pages = {17084 -- 17090}, year = {2020}, abstract = {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.}, language = {en} } @article{WuDinkelbachKerneretal.2022, author = {Wu, Zhu and Dinkelbach, Fabian and Kerner, Florian and Friedrich, Alexandra and Ji, Lei and Stepanenko, Vladimir and W{\"u}rthner, Frank and Marian, Christel M. and Marder, Todd B.}, title = {Aggregation-Induced Dual Phosphorescence from (o-Bromophenyl)-Bis(2,6-Dimethylphenyl)Borane at Room Temperature}, series = {Chemistry—A European Journal}, volume = {28}, journal = {Chemistry—A European Journal}, number = {30}, doi = {10.1002/chem.202200525}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-318297}, year = {2022}, abstract = {Designing highly efficient purely organic phosphors at room temperature remains a challenge because of fast non-radiative processes and slow intersystem crossing (ISC) rates. The majority of them emit only single component phosphorescence. Herein, we have prepared 3 isomers (o, m, p-bromophenyl)-bis(2,6-dimethylphenyl)boranes. Among the 3 isomers (o-, m- and p-BrTAB) synthesized, the ortho-one is the only one which shows dual phosphorescence, with a short lifetime of 0.8 ms and a long lifetime of 234 ms in the crystalline state at room temperature. Based on theoretical calculations and crystal structure analysis of o-BrTAB, the short lifetime component is ascribed to the T\(^M_1\) state of the monomer which emits the higher energy phosphorescence. The long-lived, lower energy phosphorescence emission is attributed to the T\(^A_1\) state of an aggregate, with multiple intermolecular interactions existing in crystalline o-BrTAB inhibiting nonradiative decay and stabilizing the triplet states efficiently.}, language = {en} } @article{GoerlZhangStepanenkoetal.2015, author = {G{\"o}rl, Daniel and Zhang, Xin and Stepanenko, Vladimir and W{\"u}rthner, Frank}, title = {Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides}, series = {Nature Communications}, volume = {6}, journal = {Nature Communications}, number = {7009}, doi = {10.1038/ncomms8009}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-148657}, year = {2015}, abstract = {New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (A\(_{m}\)BB)\(_{n}\). The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating.}, language = {en} } @article{SanchezNayaStepanenkoMandeletal.2021, author = {Sanchez-Naya, Roberto and Stepanenko, Vladimir and Mandel, Karl and Beuerle, Florian}, title = {Modulation of Crystallinity and Optical Properties in Composite Materials Combining Iron Oxide Nanoparticles and Dye-Containing Covalent Organic Frameworks}, series = {Organic Materials}, volume = {3}, journal = {Organic Materials}, doi = {10.1055/s-0040-1722655}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-231480}, pages = {17-24}, year = {2021}, abstract = {Two series of organic-inorganic composite materials were synthesized through solvothermal imine condensation between diketopyrrolopyrrole dialdehyde DPP-1 and 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP) in the presence of varying amounts of either amino- or carboxy-functionalized superparamagnetic iron oxide nanoparticles (FeO). Whereas high FeO loading induced cross-linking of the inorganic nanoparticles by amorphous imine polymers, a lower FeO content resulted in the formation of crystalline covalent organic framework domains. All hybrid materials were analyzed by magnetization measurements, powder X-ray diffraction, electron microscopy, IR, and UV/Vis absorption spectroscopy. Crystallinity, chromophore stacking, and visible absorption features are directly correlated to the mass fraction of the components, thus allowing for a fine-tuning of materials properties.}, language = {en} } @article{WehnerRoehrStepanenkoetal.2020, author = {Wehner, Marius and R{\"o}hr, Merle Insa Silja and Stepanenko, Vladimir and W{\"u}rthner, Frank}, title = {Control of self-assembly pathways toward conglomerate and racemic supramolecular polymers}, series = {Nature Communications}, volume = {11}, journal = {Nature Communications}, doi = {10.1038/s41467-020-19189-8}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-230580}, year = {2020}, abstract = {Homo- and heterochiral aggregation during crystallization of organic molecules has significance both for fundamental questions related to the origin of life as well as for the separation of homochiral compounds from their racemates in industrial processes. Herein, we analyse these phenomena at the lowest level of hierarchy - that is the self-assembly of a racemic mixture of (R,R)- and (S,S)-PBI into 1D supramolecular polymers. By a combination of UV/vis and NMR spectroscopy as well as atomic force microscopy, we demonstrate that homochiral aggregation of the racemic mixture leads to the formation of two types of supramolecular conglomerates under kinetic control, while under thermodynamic control heterochiral aggregation is preferred, affording a racemic supramolecular polymer. FT-IR spectroscopy and quantum-chemical calculations reveal unique packing arrangements and hydrogen-bonding patterns within these supramolecular polymers. Time-, concentration- and temperature-dependent UV/vis experiments provide further insights into the kinetic and thermodynamic control of the conglomerate and racemic supramolecular polymer formation. Homo- and heterochiral aggregation is a process of interest to prebiotic and chiral separation chemistry. Here, the authors analyze the self-assembly of a racemic mixture into 1D supramolecular polymers and find homochiral aggregation into conglomerates under kinetic control, while under thermodynamic control a racemic polymer is formed.}, language = {en} } @article{SchlossarekStepanenkoBeuerleetal.2022, author = {Schlossarek, Tim and Stepanenko, Vladimir and Beuerle, Florian and W{\"u}rthner, Frank}, title = {Self-assembled Ru(bda) Coordination Oligomers as Efficient Catalysts for Visible Light-Driven Water Oxidation in Pure Water}, series = {Angewandte Chemie International Edition}, volume = {61}, journal = {Angewandte Chemie International Edition}, number = {52}, doi = {10.1002/anie.202211445}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-312184}, year = {2022}, abstract = {Water-soluble multinuclear complexes based on ruthenium 2,2′-bipyridine-6,6′-dicarboxylate (bda) and ditopic bipyridine linker units are investigated in three-component visible light-driven water oxidation catalysis. Systematic studies revealed a strong enhancement of the catalytic efficiency in the absence of organic co-solvents and with increasing oligomer length. In-depth kinetic and morphological investigations suggest that the enhanced performance is induced by the self-assembly of linear Ru(bda) oligomers into aggregated superstructures. The obtained turnover frequencies (up to 14.9 s\(^{-1}\)) and turnover numbers (more than 1000) per ruthenium center are the highest reported so far for Ru(bda)-based photocatalytic water oxidation systems.}, language = {en} }