Sequential Construction Strategy for Rational Design of Luminescent Iridacycles

详细信息    查看全文

• 作者：Hui Xu ; Zi-Ao Huang ; Xugeng Guo ; Yuhui Yang ; Yuhui Hua ; Zexing Cao ; Shunhua Li ; Haiping Xia
• 刊名：Organometallics
• 出版年：2015
• 出版时间：September 14, 2015
• 年：2015
• 卷：34
• 期：17
• 页码：4229-4237
• 全文大小：587K
• ISSN：1520-6041

文摘

A convenient and general strategy has been developed to synthesize stable iridapolycycles 5鈥?b>8. Reaction of arylacetylenes with iridium-hydride complex [IrH(CO)Cl(PPh₃)₃]BF₄ via nucleophilic addition, oxidative decarbonylation, and C鈥揌 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鈥?dipyridyl to give intensely luminescent Ir(III) complex 9 bearing one C^{鈭?/sup>C and one N鈭?/sup>N ligands. Density functional theory (DFT) calculations reveal that the lowest unoccupied molecular orbitals (LUMOs) of iridapolycycles 5鈥?b>8 are located on the phosphonium groups while the highest occupied molecular orbitals (HOMOs) are mainly located on the metal-embedded C鈭?/sup>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鈭?/sup>C and N鈭?/sup>N moieties independently.}