Unravelling the conformations of di-(perylene bisimide acrylate) by combining time-resolved fluorescence-anisotropy experiments and molecular modelling

Abstract

We compare the results from time-resolved fluorescence anisotropy experiments and molecular modelling on perylene bisimide acrylate dimers which allows us to connect the observed spectral signatures unambiguously with the non-stacked and two (parallel and anti-parallel) stacked conformations. For the parallel stacked conformation the experimental data can be reproduced quantitatively using a model that assumes structural relaxation in the electronically excited state of the stacked aggregate. For the non-stacked conformation we find quantitative agreement between experiment and modelling only if a fast hopping of the electronic excitation between the perylene bisimide subunits is taken into account.

Bay-Linked Perylenediimides are Two Molecules in One: Insights from Ultrafast Spectroscopy, Temperature Dependence, and Time-Dependent Density Functional Theory Calculations

“…Because of their large exposed π surface, PDIs are particularly prone to aggregation, allowing the chromophores on neighboring PDI molecules to interact. , The magnitude of the coupling between neighboring molecules depends strongly on their relative orientation. This is explained by the elegant theory developed by Kasha and co-workers, , which is outlined in Figure b: when the long axes of the two chromophores’ transition dipoles are arranged in parallel, H-aggregate behavior (red-shifted emission with low quantum yield) results, whereas a head-to-tail configuration of the transition dipoles leads to J-aggregate behavior (blue-shifted emission with higher quantum yield). ,, …”

“…This is explained by the elegant theory developed by Kasha and co-workers, 26,27 which is outlined in Figure 1b: when the long axes of the two chromophores' transition dipoles are arranged in parallel, H- aggregate behavior (red-shifted emission with low quantum yield) results, whereas a head-to-tail configuration of the transition dipoles leads to J-aggregate behavior (blue-shifted emission with higher quantum yield). 19,28,29 The simplest type of H-or J-aggregate behavior holds only for ideal molecular geometries and for crystal structures/ dimers that have only one molecule per unit cell. However, outside of ideal conditions, both types of aggregation can emerge because of simultaneous coupling along multiple axes.…”

Dynamic Stacking Pathway of Perylene Dimers in Aromatic and Nonaromatic Solvents

“…19,32 We start by considering the dimer solvated in toluene (red curve). There is a 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 bisimide: for a slightly different structure of the PBMs (two additional benzene molecules and no connecting carbon chain) the free energy change was obtained as 15.8 kJ/mol for the solvent toluene.…”

ESA-CF Synthesis of Linear and Cyclic Polymers Having Densely Appended Perylene Units and Topology Effects on Their Thin-Film Electron Mobility

“…13−18 Accordingly, we have newly prepared a pair of topologically contrastive, linear and cyclic polymers having densely appended perylene diimide (PDI) units, to explore any topology effects in their thin-film electron carrier mobility. A class of linear polymers having pendant PDI units of unique physico-and electrochemical properties 19 have been a subject of extensive studies, covering their photophysical properties, 20,21 microphase separation, 22 and electrophysical characteristics. 23 Besides, the thin-film electron carrier mobility is of an particular interest in the fabrication of optoelectronic devices, like organic solar cells and organic light-emitting devices.…”

“…Notably, in particular, cyclic polymers having densely appended functional groups could provide a unique opportunity to attain amplified topology effects through the accumulation of the interaction between pendant functional groups, as reported in cyclic graft copolymers. − Accordingly, we have newly prepared a pair of topologically contrastive, linear and cyclic polymers having densely appended perylene diimide (PDI) units, to explore any topology effects in their thin-film electron carrier mobility. A class of linear polymers having pendant PDI units of unique physico- and electrochemical properties have been a subject of extensive studies, covering their photophysical properties, , microphase separation, and electrophysical characteristics . Besides, the thin-film electron carrier mobility is of an particular interest in the fabrication of optoelectronic devices, like organic solar cells and organic light-emitting devices. , Though the electron carrier mobility property is known to be tunable either through the molecular designing, the π-extension by the polymerization of semiconducting units, or crystallization/self-assembly techniques, − an alternative means to tune the device performance could be realized by the polymer topology effects with cyclic/cyclized polymers.…”