@article{HerbstSoberatsLeowanawatetal.2018, author = {Herbst, Stefanie and Soberats, Bartolome and Leowanawat, Pawaret and Stolte, Matthias and Lehmann, Matthias and W{\"u}rthner, Frank}, title = {Self-assembly of multi-stranded perylene dye J-aggregates in columnar liquid-crystalline phases}, series = {Nature Communications}, volume = {9}, journal = {Nature Communications}, doi = {10.1038/s41467-018-05018-6}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-319914}, year = {2018}, abstract = {Many discoid dyes self-assemble into columnar liquid-crystalline (LC) phases with packing arrangements that are undesired for photonic applications due to H-type exciton coupling. Here, we report a series of crystalline and LC perylene bisimides (PBIs) self-assembling into single or multi-stranded (two, three, and four strands) aggregates with predominant J-type exciton coupling. These differences in the supramolecular packing and optical properties are achieved by molecular design variations of tetra-bay phenoxy-dendronized PBIs with two N-H groups at the imide positions. The self-assembly is driven by hydrogen bonding, slipped π-π stacking, nanosegregation, and steric requirements of the peripheral building blocks. We could determine the impact of the packing motifs on the spectroscopic properties and demonstrate different J- and H-type coupling contributions between the chromophores. Our findings on structure-property relationships and strong J-couplings in bulk LC materials open a new avenue in the molecular engineering of PBI J-aggregates with prospective applications in photonics.}, 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} }