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Self‐Sorting Supramolecular Polymerization: Helical and Lamellar Aggregates of Tetra‐Bay‐Acyloxy Perylene Bisimide
Author(s) -
Hecht Markus,
Leowanawat Pawaret,
Gerlach Tabea,
Stepanenko Vladimir,
Stolte Matthias,
Lehmann Matthias,
Würthner Frank
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202006744
Subject(s) - perylene , chemistry , supramolecular chemistry , lamellar structure , supramolecular polymers , monomer , polymerization , self assembly , quantum yield , hydrogen bond , photochemistry , imide , crystallography , dissociation (chemistry) , pyrene , polymer chemistry , fluorescence , polymer , molecule , crystal structure , organic chemistry , physics , quantum mechanics
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.