Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity Size

Jessica Rühe; David Bialas; Peter Spenst; Ana-Maria Krause; Frank Würthner

doi:10.1055/s-0040-1709998

CC BY-NC-ND 4.0 · Organic Materials 2020; 02(02): 149-158
DOI: 10.1055/s-0040-1709998

Original Article

The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes, or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/). (2020) The Author(s).

Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity Size

Jessica Rühe

^aInstitut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany

,

David Bialas

^aInstitut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany

,

Peter Spenst

^aInstitut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany

,

Ana-Maria Krause

^bCenter for Nanosystems Chemistry, Universität Würzburg, Theodor-Boveri-Weg, 97074 Würzburg, Germany

,

Frank Würthner

^aInstitut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany

^bCenter for Nanosystems Chemistry, Universität Würzburg, Theodor-Boveri-Weg, 97074 Würzburg, Germany

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Abstract

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Abstract

Five cyclophanes composed of two perylene bisimide (PBI) dyes and various CH₂–arylene–CH₂ linker units were synthesized. PM6-D3H4 geometry-optimized structures and a single crystal for one of these cyclophanes reveal well-defined distances between the two coplanar PBI units in these cyclophanes, spanning the range from 5.0 to 12.5 Å. UV/vis absorption spectra reveal a redistribution of oscillator strength of the vibronic bands due to a H-type exciton coupling even for the cyclophane with the largest interchromophoric distance. A quantitative evaluation according to the Kasha–Spano theory affords exciton coupling strengths ranging from 64 cm⁻¹ for the largest cyclophane up to 333 cm⁻¹ for the smallest one and a surprisingly good fit to the cubic interchromophoric distance in the framework of the point-dipole approximation. Interchromophoric interaction is also noticed in fluorescence lifetimes that are significantly increased for all five cyclophanes as expected for H-coupled chromophores due to a decrease of the radiative rate. For the three largest cyclophanes with interchromophoric distances of >9 Å, fluorescence quantum yields remain high in chloroform (>88%), whilst for the smaller ones with interchromophoric distances <6 Å, additional nonradiative pathways lead to a pronounced fluorescence quenching.

Key words

cyclophanes - exciton coupling - fluorescence - organic dyes

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Referenzen

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