Structure and Spectroscopic Properties of Gold(I) Diselenophosph(in)ate Complexes: A Joint Experimental and Theoretical Study
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- 作者：Camille Latouche ; Yu-Chen Lee ; Jian-Hong Liao ; Eric Furet ; Jean-Yves Saillard ; C. W. Liu ; Abdou Boucekkine
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：November 5, 2012
- 年：2012
- 卷：51
- 期：21
- 页码：11851-11859
- 全文大小：408K
- 年卷期：v.51,no.21(November 5, 2012)
- ISSN：1520-510X
文摘
The structure and optical properties of several polynuclear gold(I) species, namely, diselenophosphate [Au{渭-Se2P(OR)2}]2 complexes (R = iPr, Et, nPr) respectively numbered 1, 2, and 3 and number 4 [Au{渭-Se2P(CH2)2Ph)2}]2, exhibiting interesting structural, absorption, and emission properties have been studied. The synthesis, full characterization, and experimental spectroscopic study of 3 and 4 have first been carried out, 1 and 2 being previously studied. In the solid state, 3 gives polymers, like 1 and 2, whereas 4 exists under a dinuclear monomeric form. The absorption and phosphorescence properties of 4 have been rationalized using DFT and TDDFT computations. In particular, Au鈥揂u bonding seems to appear in its first singlet and triplet states, whereas such a bond does not exist in the ground state. Then, the influence of polymerization through aurophilic bonding on the optical properties of 2 is investigated (1 and 3 behave as 2). It is shown using TDDFT computations that its observed UV鈥搗isible excitation spectrum in solution is due to high oligomers and not to monomers or low size oligomers. ESI-MS molecular weight measurements confirm the occurrence of such oligomers of 2 in solution. An assignment of the observed bands of 2 is proposed. The transition corresponding to the first excitation band, which is mainly a HOMO to LUMO one, exhibits metal-centered character, i.e., a gold 5d to 6p orbital transition, but concomitantly transfers significant electron density from gold to phosphorus atoms so that it is also a MLCT one.