Encapsulating Iodine and Copper into Copper(I) Clusters Stabilized by Dichalcogenolate Ligands: Stability, Structure, and Optical Properties
Encapsulating Iodine and Copper into Copper(I) Clusters Stabilized by Dichalcogenolate Ligands: Stability, Structure, and Optical Properties
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DOI：
10.1021/acs.inorgchem.7b02269
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发表时间：
2017-11-20
影响因子：
4.6
通讯作者：
Saillard, Jean-Yves
中科院分区：
文献类型：
--
作者：
Latouche, Camille;Liao, Jian-Hong;Saillard, Jean-Yves
用密度泛函理论（DFT）研究了十一、十二核铜（I）团簇的稳定性，并与二硫代和二硒代磷酸盐进行了比较.提供了一个键合分析，这表明碘化物和它的主机之间的强离子共价键合。标题化合物的电子结构表明有趣的光致发光性质的可能性，这是充分研究了含时DFT计算，包括振动的贡献，模拟磷光光谱。本文报道了[Cu-11（mu（9）-I）（mu（3）-I）（3）{Se_2 P（（OPr）-Pr_i）（2）}（6）]（+）和[Cu-11（mu（9）-I）（mu（3）-I）（3）（Se_2 PPh_2）（6）]（+）的合成、X射线结构和全部表征。从这种结合的理论/实验研究中，提出了由形式上Cu-阴离子的相同铜（I）笼包封也是可能的。密度泛函理论的计算结果与稳定的双电子超原子的存在是一致的。
The stability of large ligated copper(I) clusters of undeca; and, dodecanuclearity encapsulating iodide and stabilized by dithio- and diseleno-phosph(in)ates was investigated by density functional theory (DFT) calculations. A bonding analysis is provided, which shows strong iono-covalent bonding between the iodide and its host. The electronic structures of the title compounds suggest the possibility for interesting photoluminescent properties, which were fully investigated by time-dependent DFT calculations including vibronic contributions to, simulate the phosphorescence spectra. The quantum mechanical results were compared to the experimental data "obtained for the new clusters [Cu-11(mu(9)-I)(mu(3)-I)(3){Se2P((OPr)-Pr-i)(2)}(6)](+) and [Cu-11(mu(9)-I)(mu(3)-I)(3)(Se2PPh2)(6])(+) whose syntheses, X-ray structures, and full characterizations are reported in this paper. From this combined theoietical/experimental investigation, it is suggested that the encapsulation by the same copper(I) cages of a formally Cu- anion is also possible. DFT calculations on these species are consistent with the existence of stable two-electron superatoms.