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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 E → Z 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.

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

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