TY  - JOUR
A1  - Görl, Daniel
A1  - Zhang, Xin
A1  - Stepanenko, Vladimir
A1  - Würthner, Frank
T1  - Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides
JF  - Nature Communications
N2  - 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.
KW  - cylindrical micelles
KW  - water
KW  - amplification
KW  - association
KW  - emission
KW  - organization
KW  - polymerization
KW  - dyes
KW  - fluorescent
KW  - aqueous medium
Y1  - 2015
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-148657
VL  - 6
IS  - 7009
ER  - 
TY  - JOUR
A1  - Grande, Vincenzo
A1  - Soberats, Bartolome
A1  - Herbst, Stefanie
A1  - Stepanenko, Vladimir
A1  - Würthner, Frank
T1  - Hydrogen-bonded perylene bisimide J-aggregate aqua material
N2  - 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.
KW  - self-assembly
KW  - dyes
KW  - aqua material
Y1  - 2018
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-204715
UR  - https://doi.org/10.1039/C8SC02409J
SN  - 2041-6539
VL  - 9
ER  - 
TY  - JOUR
A1  - Schmidt, David
A1  - Stolte, Matthias
A1  - Süß, Jasmin
A1  - Liess, Dr. Andreas
A1  - Stepanenko, Vladimir
A1  - Würthner, Frank
T1  - Protein-like enwrapped perylene bisimide chromophore as bright microcrystalline emitter material
JF  - Angewandte Chemie International Edition
N2  - Strongly emissive solid‐state materials are mandatory components for many emerging optoelectronic technologies, but fluorescence is often quenched in the solid state owing to strong intermolecular interactions. The design of new organic pigments, which retain their optical properties despite their high tendency to crystallize, could overcome such limitations. Herein, we show a new material with monomer‐like absorption and emission profiles as well as fluorescence quantum yields over 90 % in its crystalline solid state. The material was synthesized by attaching two bulky tris(4‐tert‐butylphenyl)phenoxy substituents at the perylene bisimide bay positions. These substituents direct a packing arrangement with full enwrapping of the chromophore and unidirectional chromophore alignment within the crystal lattice to afford optical properties that resemble those of their natural pigment counterparts, in which chromophores are rigidly embedded in protein environments.
KW  - cristal engeneering
KW  - dyes
KW  - flourescence quantum yield
KW  - perylene bisimides
KW  - solid-state emitters
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-204809
VL  - 58
IS  - 38
ER  -