Issue 46, 2022

A photo-switchable molecular capsule: sequential photoinduced processes

Abstract

The metastable trilacunary heteropolyoxomolybdate [PMo9O31(py)3]3−{PMo9}; py = pyridine) and the ditopic pyridyl bearing diarylethene (DAE) (C25H16N2F6S2) self-assemble via a facile ligand replacement methodology to yield the photo-active molecular capsule [(PMo9O31)2(DAE)3]6−. The spatial arrangement and conformation of the three DAE ligands are directed by the surface chemistry of the molecular metal oxide precursor with exclusive ligation of the photo-active antiparallel rotamer to the polyoxometalate (POM) while the integrity of the assembly in solution has been verified by a suite of spectroscopic techniques. Electrocyclisation of the three DAEs occurs sequentially and has been investigated using a combination of steady-state and time-resolved spectroscopies with the discovery of a photochemical cascade whereby rapid photoinduced ring closure is followed by electron transfer from the ring-closed DAE to the POM in the latent donor–acceptor system on subsequent excitation. This interpretation is also supported by computational and detailed spectroelectrochemical analysis. Ring-closing quantum yields were also determined using a custom quantum yield determination setup (QYDS), providing insight into the impact of POM coordination on these processes.

Graphical abstract: A photo-switchable molecular capsule: sequential photoinduced processes

Supplementary files

Article information

Article type
Edge Article
Submitted
18 aug 2022
Accepted
21 okt 2022
First published
24 okt 2022
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., 2022,13, 13732-13740

A photo-switchable molecular capsule: sequential photoinduced processes

M. Choudhari, J. Xu, A. I. McKay, C. Guerrin, C. Forsyth, H. Z. Ma, L. Goerigk, R. A. J. O'Hair, A. Bonnefont, L. Ruhlmann, S. Aloise and C. Ritchie, Chem. Sci., 2022, 13, 13732 DOI: 10.1039/D2SC04613J

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