Crystal Engineering of 1D Exciton Systems Composed of Single‐ and Double‐Stranded Perylene Bisimide J‐Aggregates

Matthias Stolte,Reinhard Hecht,Astrid Kudzus,Linlin Liu,David Schmidt,Frank Würthner,Christina Kaufmann,Zengqi Xie

doi:10.1002/adom.202000926

Matthias Stolte, Reinhard Hecht + Show 6 more

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https://doi.org/10.1002/adom.202000926

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Abstract

AbstractSingle crystals of three at bay area tetraphenoxy‐substituted perylene bisimide dyes are grown by vacuum sublimation. X‐ray analysis reveals the self‐assembly of these highly twisted perylene bisimides (PBIs) in the solid state via imide–imide hydrogen bonding into hydrogen‐bonded PBI chains. The crystallographic insights disclose that the conformation and sterical congestion imparted by the phenoxy substituents can be controlled by ortho‐substituents. Accordingly, whilst sterically less demanding methyl and isopropyl substituents afford double‐stranded PBI chains of complementary P and M atropo‐enantiomers, single hydrogen‐bonded chains of homochiral PBIs are observed for the sterically more demanding ortho‐phenyl substituents. Investigation of the absorption and fluorescence properties of microcrystals and thin films of these PBIs allow for an unambiguous interpretation of these exciton systems. Thus, the J‐aggregates of the double‐stranded crystals exhibit a much larger (negative) exciton coupling than the single‐stranded one, which in contrast has the higher solid‐state fluorescence quantum yield.

Highlights

Introduction ment of theperylene bisimides (PBIs), entirely different photophysical properties can be tailored.[18,19,20] These insights from small model sys-Crystal engineering of π-scaffolds in general[1,2,3,4,5,6] and of perylene tems motivate the engineering of unprecedented PBI bisimides (PBIs) in particular[7,8,9] has a long tradition
Institut für Organische Chemie Universität Würzburg Am Hubland, Würzburg 97074, Germany E-mail: wuerthner@uni-wuerzburg.de bathochromic shifts of the absorption and emission bands and high exciton mobilities originating from J-type exciton coupling.[26]
The aim of this work was to engineer a slip-stacked packing arrangement of PBI dyes to afford a new class of PBI pigments with solid-state properties that are dis

Summary

Introduction

Introduction ment of thePBIs, entirely different photophysical properties can be tailored.[18,19,20] These insights from small model sys-Crystal engineering of π-scaffolds in general[1,2,3,4,5,6] and of perylene tems motivate the engineering of unprecedented PBI bisimides (PBIs) in particular[7,8,9] has a long tradition. PBIs, entirely different photophysical properties can be tailored.[18,19,20] These insights from small model sys-. For several packing arrangements in solid-state materials with the goal decades PBI functional material research was focused on the to tailor functional properties for applications of these dyes beyond their conventional ones as color pigments.[21,22,23,24,25] Here. F. Würthner of particular interest is the longitudinal slip-stack arrangement of the dyes that affords dye aggregates with significant bathochromic shifts of the absorption and emission bands and high exciton mobilities originating from J-type exciton coupling.[26] the aim of this work was to engineer a slip-stacked packing arrangement of PBI dyes to afford a new class of PBI pigments with solid-state properties that are dis-

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