Issue 41, 2022

Synthesis, structural studies, and photophysical properties of heteroleptic inverse-coordination clusters

Abstract

Two series of hyper-coordinated halide-centered M12 cuboctahedral clusters, [M1212-X){S2P(OnPr)2}6{C[triple bond, length as m-dash]CPh}4](PF6), 1a–c and 2a–c (where M = Cu, 1; Ag, 2; X = Cl, a; Br, b; I, c), were synthesized and fully characterized by ESI-MS, multi-NMR spectroscopy, IR and UV-Vis spectroscopy, photoluminescence analysis, and single-crystal X-ray crystallography. Structures 1c, 2b, and 2c show a twelve-coordinated halide encapsulated in the M12 cage, which is stabilized by six dithiophosphate and four alkynyl ligands. Compound 2b is the first Ag(I) cluster containing a twelve-coordinated bromide. The structural features of all six clusters are highly similar, providing a comparison basis of the inverse coordination for halides. Besides, the detailed structural analysis illustrates how the inverse coordination of a halide has influenced the size of the cuboctahedral M12 framework.

Graphical abstract: Synthesis, structural studies, and photophysical properties of heteroleptic inverse-coordination clusters

Supplementary files

Article information

Article type
Paper
Submitted
30 Jun 2022
Accepted
15 Sep 2022
First published
16 Sep 2022

Dalton Trans., 2022,51, 15903-15911

Synthesis, structural studies, and photophysical properties of heteroleptic inverse-coordination clusters

G. Huang, R. P. B. Silalahi, J. Liao, T. Chiu and C. W. Liu, Dalton Trans., 2022, 51, 15903 DOI: 10.1039/D2DT02100E

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