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Issue 42, 2018
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Structure-switching M3L2 Ir(iii) coordination cages with photo-isomerising azo-aromatic linkers

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Abstract

Cyclotriguaiacylene has been functionalised with 3- or 4-pyridyl-azo-phenyl groups to form a series of molecular hosts with three azobenzene-type groups that exhibit reversible photo-isomerisation. Reaction of the host molecules with [Ir(C^N)2(NCMe)2]+ where C^N is the cyclometallating 2-phenylpyridinato, 2-(4-methylphenyl)pyridinato or 2-(4,5,6-trifluorophenyl)pyridinato results in the self-assembly of a family of five different [{Ir(C^N)2}3(L)2]3+ coordination cages. Photo-irradiation of each of the cages with a high energy laser results in EZ photo-isomerisation of the pyridyl-azo-phenyl groups with up to 40% of groups isomerising. Isomerisation can be reversed by exposure to blue light. Thus, the cages show reversible structure-switching while maintaining their compositional integrity. This represents the largest photo-induced structural change yet reported for a structurally-integral component of a coordination cage. Energy minimised molecular models indicate a switched cage has a smaller internal space than the initial all-E isomer. The [Ir(C^N)2(NCMe)2]+ cages are weakly emissive, each with a deep blue luminescence at ca. 450 nm.

Graphical abstract: Structure-switching M3L2 Ir(iii) coordination cages with photo-isomerising azo-aromatic linkers

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Supplementary files

Article information


Submitted
06 Aug 2018
Accepted
29 Aug 2018
First published
06 Sep 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 8150-8159
Article type
Edge Article

Structure-switching M3L2 Ir(III) coordination cages with photo-isomerising azo-aromatic linkers

S. Oldknow, D. R. Martir, V. E. Pritchard, M. A. Blitz, Colin W. G. Fishwick, E. Zysman-Colman and M. J. Hardie, Chem. Sci., 2018, 9, 8150
DOI: 10.1039/C8SC03499K

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