Journal
DALTON TRANSACTIONS
Volume -, Issue 4, Pages 623-631Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/b313638h
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The utility of Suzuki cross-coupling methodology for the in situ elaboration of bromo-functionalised bis-terpyridyl iridium(III) complexes has been explored. The complex [Ir(tpy)(tpy-phi-Br)](3+) {tpy-phi-Br = 4'-(4-bromophenyl)-2,2':6',2-terpyridine} undergoes palladium-catalysed cross-coupling with aryl boronic acids to yield biaryl-substituted complexes directly. The biphenyl and 4-cyanobiphenyl-substituted products display relatively intense, long-lived (tau > 100 mus) yellow emission in degassed aqueous solution at room temperature, assigned to a (3)pi-pi* state. A 4-aminobiphenyl-substituted analogue displays an additional low energy absorbance band, attributed to an intraligand charge-transfer (ILCT) excited state, and is scarcely emissive under the same conditions. The iridium(III) complex of 4'-mesityl-terpyridine is also reported. Its emission is much shorter-lived, with a spectral profile resembling that of unsubstituted [Ir(tpy)(2)](3+), confirming the need for the attainment of a roughly coplanar geometry for stabilisation of the (3)pi-pi* excited state.
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