Crystal Engineering of 1D Exciton Systems Composed of Single‐ and Double‐Stranded Perylene Bisimide J‐Aggregates. Issue 18 (25th June 2020)

• Record Type: Journal Article
• Authors: Stolte, Matthias; Hecht, Reinhard; Xie, Zengqi; Liu, Linlin; Kaufmann, Christina; Kudzus, Astrid; Schmidt, David; Würthner, Frank
• Is Part Of: Advanced optical materials. Volume 8:Issue 18(2020)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2020-06-25
• Subjects: fluorescence -- J‐aggregates -- perylene bisimides -- reabsorption -- single crystal structure; Optical materials -- Periodicals; Photonics -- Periodicals; 620.11295
• DOI: 10.1002/adom.202000926
• Languages: English
• ISSNs: 2195-1071

Abstract

Abstract: Single 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. Abstract : Three tetraphenoxy‐substituted perylene bisimide dyes self‐assemble in their crystalline solid state via hydrogen bonds into single‐ and double‐stranded J‐aggregates. Absorption and emission spectra for solutions and (poly‐)crystalline powders up to microcrystals reveal the impact of these two distinct supramolecular arrangements on optical properties. Solid‐state fluorescence quantum yields of up to 59% are observed for single‐stranded chains.