Synthesis, Structures, and Luminescence Properties of Interconvertible AuI2ZnII and AuI3ZnII Complexes with Mixed Bis(diphenylphosphin
详细信息 查看全文
- 作者：Yuji Hashimoto ; Nobuto Yoshinari ; Daisuke Naruse ; Koichi Nozaki ; Takumi Konno
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：December 16, 2013
- 年：2013
- 卷：52
- 期：24
- 页码：14368-14375
- 全文大小：397K
- 年卷期：v.52,no.24(December 16, 2013)
- ISSN：1520-510X
文摘
The reaction of the digold(I) complex [Au2(dppm)(d-pen)2]2鈥?/sup> ([1]2鈥?/sup>; dppm = bis(diphenylphosphino)methane and d-pen = d-penicillaminate) with Zn2+ in a 1:1 ratio gave the heterometallic AuI2ZnII trinuclear complex [Au2Zn(dppm)(d-pen)2] ([3]), in which the Zn2+ ion is coordinated by [1]2鈥?/sup> in an N2O2S2 octahedral geometry with the trans(O) configuration, forming an 8-membered Au2ZnS2P2C metalloring. A similar reaction using the newly prepared and crystallographically characterized trigold(I) complex [Au3(dppm)2(d-pen)2]鈭?/sup> ([2]鈭?/sup>) produced the AuI3ZnII tetranuclear complex [Au3Zn(dppm)2(d-pen)2]+ ([4]+), in which the Zn2+ ion is coordinated by [2]鈭?/sup> in a similar octahedral geometry to form a Au3ZnS2P4C2 12-membered metalloring. Complex [3] was converted to [4]+ by treatment with [Au2(dppm)2]2+ in a 2:1 ratio, whereas [4]+ reverted to [3] upon treatment with a mixture of [Au(d-pen)2]2鈥?/sup> and Zn2+ in a 1:1 ratio, indicative of the facile insertion/removal of the [Au(dppm)]+ moiety with retention of the geometry of the trans(O)-[Zn(d-pen-N,O,S)2]2鈥?/sup> unit. An analogous interconversion that requires the insertion/removal of the [Au(dppm)]+ moiety was also recognized between [1]2鈥?/sup> and [2]鈭?/sup>. NMR spectroscopy revealed that [4]+ is in equilibrium with [3] and [Au2(dppm)2]2+ in solution, the ratio of which is largely dependent on the solvent polarity. The luminescence properties of these complexes were also investigated, revealing the importance of the intramolecular aurophilic interaction, as well as the ZnII coordination, for enhancement of the emission quantum efficiencies.