The hexanuclear rhenium cluster ions Re6S8X64− (X=Cl, Br, I): Are these clusters luminescent?
The hexanuclear rhenium cluster ions Re6S8X64− (X=Cl, Br, I): Are these clusters luminescent?
复制标题
六核铼簇离子 Re6S8X64− (X=Cl, Br, I)：这些簇发光吗？
DOI：
10.1063/1.477958
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发表时间：
1999
影响因子：
4.4
通讯作者：
Lucı́a Hernández
中科院分区：
文献类型：
--
作者：
R. Arratia‐Pérez;Lucı́a Hernández
本文报道了八面体Re 6S 8X 64-（X=Cl，Br，I）团簇的Dirac分子轨道计算结果.计算的相对论分子轨道表明，团簇的最高占据轨道主要集中在末端卤代配体上，其中μ3-S配体也有贡献.所有三个六核双金属簇离子都具有单重基态（跨越Γ6+对称性），因此是抗磁性的。它们具有与强烈发光的W 6Cl 142 −团簇离子相同的基态和激发态特征。计算的电荷分布表明，这些团簇可以分别表示为：Re 6 - 0.21S8 - 0.16Cl6 - 0.24，Re 6 - 0.23S8 - 0.17Br6 - 0.21和Re 6 - 0.26S8 - 0.26I6 - 0.12。
Dirac molecular orbital calculations on the octahedral rhenium clusters Re6S8X64− (where X=Cl, Br, I) are reported. The calculated relativistic molecular orbitals indicate that the manifold of closely spaced unoccupied energy levels are mainly localized on the octahedral rhenium core with some contributions from the μ3-S ligands, while all the cluster highest occupied molecular orbitals are largely centered on the terminal halide ligands. All three hexanuclear rhenium cluster ions have singlet ground state (spanning the Γ6+ symmetry) and are therefore diamagnetic. They have the same ground state and excited state features as the intensely luminescent W6Cl142− cluster ion. The calculated charge distributions indicate that these clusters could be formulated as: Re6−0.21S8−0.16Cl6−0.24, Re6−0.23S8−0.17Br6−0.21 and Re6−0.26S8−0.26I6−0.12, respectively.