Spectroscopic studies on linear-chain semiconductors and related species. Vibrational and resonance Raman spectroscopy of the diphosphite complexes K4[Pt2(pop)4]•2H2O, K4[Pt2(pop)4X2]•2H2O, and K4[Pt2(pop)4X]•nH2O, X=Cl, Br, I
Spectroscopic studies on linear-chain semiconductors and related species. Vibrational and resonance Raman spectroscopy of the diphosphite complexes K4[Pt2(pop)4]•2H2O, K4[Pt2(pop)4X2]•2H2O, and K4[Pt2(pop)4X]•nH2O, X=Cl, Br, I
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线性链半导体和相关物质的光谱研究 二亚磷酸酯配合物 K4[Pt2(pop)4]•2H2O、K4[Pt2(pop)4X2]•2H2O 和 K4[Pt2(pop)4X 的振动和共振拉曼光谱。 ]•nH2O, X=Cl, Br, I
DOI：
10.1021/ic00219a045
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发表时间：
1985
影响因子：
4.6
通讯作者：
R. Clark
中科院分区：
文献类型：
--
作者：
M. Kurmoo;R. Clark
对二亚磷酸酯配合物K4 [Pt2 (pop) 4]-2H20、K4 [Pt2 (pop) 4X2]-2H20和K4 [Pt2 (pop) 4X]-nH20， X= Cl, Br， I进行了电子、红外、拉曼，特别是共振拉曼的研究。这些结果为K4 [Pt2 (pop) 4]-2H20到'A2u* Alg的最低允许电子跃迁提供了独立的确认。拉曼光谱，特别是K4 [Pt2 (pop) 4I2]-2H20，在最低电子跃迁的共振中，由vt（»<(PtPt)）的长，接近谐波的过程组成，在这种情况下达到\2vt（«[= 105.0±0.5 cm'1, xn< 0.1 cm'1）。链式聚合物K4 [Pt2 (pop) 4X]- nh20的电子能谱在低波数端由一个Ptm<- Pt11的价间带支配。与价间带共振的拉曼光谱表明，氯链是一个具有非常不对称桥接氯原子的局域价物质，独立的晶体学证实了这一点。光谱学和晶体学结果表明，链溴和链碘是具有几乎对称卤素桥的近离域价态。
Electronic, infrared, Raman, and, in particular, resonance Raman studies of the diphosphite complexes K4 [Pt2 (pop) 4]-2H20, K4 [Pt2 (pop) 4X2]-2H20, and K4 [Pt2 (pop) 4X]-nH20, X= Cl, Br, I, have been carried out. The results provide independent confirmation of the assignment of the lowest allowed electronic transition of K4 [Pt2 (pop) 4]-2H20 to'A2u* Alg. The Raman spectra, inparticular of K4 [Pt2 (pop) 4I2]-2H20, consist of long, nearly harmonic progressions in vt (»<(PtPt)) at resonance with the lowest electronic transition, reaching in this case as far as\2vt («[= 105.0±0.5 cm'1, xn< 0.1 cm'1). The electronic spectra of the chain polymers, K4 [Pt2 (pop) 4X]-nH20, are dominated at the low-wavenumber end by a Ptm<- Pt11 intervalence band in each case. Raman spectra taken at resonance with the intervalence band indicate that the chain chloride is a localized-valence species with very asymmetrically bridging chlorine atoms, as independently confirmed crystallographically. Both spectroscopic and crystallographic results indicate that the chain bromide and chain iodide are much more nearly delocalized valence species with nearly symmetric halogen bridges.