Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu4 and Au@Ag4 Clusters Supported by tris(2-Pyridyl)phosphine

被引：13

作者：

Baranov, Andrey Yu. ^{[1
]}

Slavova, Sofia O. ^{[2
]}

Berezin, Alexey S. ^{[1
]}

Petrovskii, Stanislav K. ^{[2
]}

Samsonenko, Denis G. ^{[1
]}

Bagryanskaya, Irina Yu. ^{[3
]}

Fedin, Vladimir P. ^{[1
]}

Grachova, Elena V. ^{[2
]}

Artem, Alexander V. ^{[1
]}

机构：

[1] Nikolaev Inst Inorgan Chem, Novosibirsk 630090, Russia

[2] Bulgarian Acad Sci, Inst Gen & Inorgan Chem, Sofia 1113, Bulgaria

[3] N N Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia

来源：

INORGANIC CHEMISTRY | 2022年 / 61卷 / 28期

基金：

俄罗斯科学基金会;

关键词：

GOLD(I)-SILVER(I) CLUSTER; METAL-COMPLEXES; GOLD; AG; PHOSPHORESCENCE; SILVER; D(8);

D O I：

10.1021/acs.inorgchem.2c01474

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

ABSTRACT: We report herein a family of polynuclear complexes, [Au@Ag4(Py3P)4]X5 and [Au@Cu4(Py3P)4]X5 [X = NO3, ClO4, OTf, BF4, SbF6], containing unprecedented Au-centered Ag4 and Cu4 tetrahedral cores supported by tris(2-pyridyl)phosphine (Py3P) ligands. The [Au@Ag4]5+ clusters are synthesized via controlled substitution of the central Ag(I) ion in all-silver [Ag@ Ag4]5+ precursors by the reaction with Au(tht)Cl, while the [Au@ Cu4]5+ cluster is assembled through the treatment of a preorganized [Au(Py3P)4]+ metallo-ligand with 4 equiv of a Cu(I) source. The structure of the Au@M4 clusters has been experimentally and theoretically investigated to reveal very weak intermolecular Au-M metallophilic interactions. At ambient temperature, the designed compounds emit a modest turquoise-to-yellow luminescence with microsecond lifetimes. Based on the temperature-dependent photophysical experiments and DFT/TD-DFT computations, the emission observed has been assigned to an MLCT or LLCT type depending on composition of the cluster core.

引用

页码：10925 / 10933

页数：9

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