Issue 3, 2017

Is energy transfer limiting multiphotochromism? answers from ab initio quantifications

Abstract

Dithienylethenes (DTEs) can be assembled to form supramolecular multiphotochromic systems that are highly functional molecular architectures of potential interest for building complex optoelectronic devices. Yet even simple DTE dimers relying on an organic linker may suffer from a partial photoactivity, i.e., only one of the two switches does isomerise. Experimentally, this limited photochromism has been attributed to an excited state energy transfer (EET) between the two DTEs of the multimer; this EET taking place instead of the desired photoinduced cyclisation of the DTE. However, no clear evidences of this phenomenon have been provided so far. In this work we propose the first rationalisation of this potential parasite photoinduced event using a computational approach based on Time-Dependent Density Functional Theory (TD-DFT) for the calculation of the electronic coupling in DTE dimers. Besides quantifying EET in several systems, we dissect the role of through-bond and through-space mechanisms on this process and clarify their dependence on both the nature and length of the bridge separating the two photochromes. The theoretical data obtained in this framework are in full agreement with the experimental outcomes and pave the way toward a molecular design of coupled, yet fully functionals, DTE-based multiswitches.

Graphical abstract: Is energy transfer limiting multiphotochromism? answers from ab initio quantifications

Supplementary files

Article information

Article type
Paper
Submitted
01 Nov 2016
Accepted
15 Dec 2016
First published
19 Dec 2016

Phys. Chem. Chem. Phys., 2017,19, 2044-2052

Is energy transfer limiting multiphotochromism? answers from ab initio quantifications

A. Fihey, R. Russo, L. Cupellini, D. Jacquemin and B. Mennucci, Phys. Chem. Chem. Phys., 2017, 19, 2044 DOI: 10.1039/C6CP07458H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements