Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu4and Au@Ag4 Clusters Supported by tris(2-Pyridyl)phosphine

Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu4and Au@Ag4 Clusters Supported by tris(2-Pyridyl)phosphine Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669

Output data

Year: 2022, Volume: 61, Number: 28, Pages: 10925-10933 Pages count : 9 DOI: 10.1021/acs.inorgchem.2c01474

Authors

Baranov Andrey Yu. ¹ , Slavova Sofia O. ² , Berezin Alexey S. ¹ , Petrovskii Stanislav K. ³ , Samsonenko Denis G. ¹ , Bagryanskaya Irina Yu. ⁴ , Fedin Vladimir P. ¹ , Grachova Elena V. ³ , Artem’ev Alexander V. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry
2	Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences
3	Institute of Chemistry, St Petersburg University
4	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry

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 pre-organized [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.

Baranov A.Y. , Slavova S.O. , Berezin A.S. , Petrovskii S.K. , Samsonenko D.G. , Bagryanskaya I.Y. , Fedin V.P. , Grachova E.V. , Artem’ev A.V.
Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu4and Au@Ag4 Clusters Supported by tris(2-Pyridyl)phosphine
Inorganic Chemistry. 2022. V.61. N28. P.10925-10933. DOI: 10.1021/acs.inorgchem.2c01474 WOS РИНЦ

Submitted:	Apr 29, 2022
Published print:	Jul 1, 2022

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