Issue 38, 2020

Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization

Abstract

Control over the photochemical outcome of photochromic molecules in solution represents a major challenge, as photoexcitation often leads to multiple competing photochemical and/or supramolecular pathways resulting in complex product mixtures. Herein, we demonstrate precise and efficient control over the photochemical behaviour of cyanostilbenes in solution using a straightforward solvent-controlled approach based on supramolecular polymerization. To this end, we designed a π-extended cyanostilbene bolaamphiphile that exhibits tuneable solvent-dependent photochemical behaviour. Photoirradiation of the system in a monomeric state (in organic solvents) exclusively leads to a highly reversible and efficient E/Z photoisomerization, whereas a nearly quantitative [2 + 2] photocycloaddition into a single cyclobutane (anti head-to-tail) occurs in aqueous solutions. These results can be rationalized by a highly regular and preorganized antiparallel J-type arrangement of the cyanostilbene units that is driven by aqueous supramolecular polymerization. The presented concept demonstrates a novel approach towards solvent-selective and environmentally friendly photochemical transformations, which is expected to broaden the scope of supramolecular polymerization.

Graphical abstract: Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization

Supplementary files

Article information

Article type
Edge Article
Submitted
22 Jun 2020
Accepted
11 Sep 2020
First published
11 Sep 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 10405-10413

Solvent-controlled E/Z isomerization vs. [2 + 2] photocycloaddition mediated by supramolecular polymerization

T. Dünnebacke, K. K. Kartha, J. M. Wiest, R. Q. Albuquerque and G. Fernández, Chem. Sci., 2020, 11, 10405 DOI: 10.1039/D0SC03442H

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