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Xu H.,Xiamen University | Huang Z.-A.,Xiamen University | Guo X.,Xiamen University | Yang Y.,Xiamen University | And 6 more authors.
Organometallics | Year: 2015

A convenient and general strategy has been developed to synthesize stable iridapolycycles 5-8. Reaction of arylacetylenes with iridium-hydride complex [IrH(CO)Cl(PPh3)3]BF4 via nucleophilic addition, oxidative decarbonylation, and C-H bond activation results in the formation of a series of iridacyclopentadiene derivatives, including benzo-iridacyclopentadiene 5, naphtho-iridacyclopentadiene 6, pyreno-iridacyclopentadiene 7, and thieno-iridacyclopentadiene 8. These iridapolycycles display high thermal and air stability yet can be further functionalized via facile ligand substitution reactions. As an example, complex 5 was used as a metallosynthon to react with 2,2′-dipyridyl to give intensely luminescent Ir(III) complex 9 bearing one C∧C and one N∧N ligands. Density functional theory (DFT) calculations reveal that the lowest unoccupied molecular orbitals (LUMOs) of iridapolycycles 5-8 are located on the phosphonium groups while the highest occupied molecular orbitals (HOMOs) are mainly located on the metal-embedded C∧C frameworks. Our method offers a sequential construction strategy for constructing luminescent iridacycles, which potentially allows facile tuning of the photoluminescence properties by modulating the C∧C and N∧N moieties independently. © 2015 American Chemical Society.

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