Journal
DALTON TRANSACTIONS
Volume 51, Issue 41, Pages 15903-15911Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2dt02100e
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- National Science and Technology Council of Taiwan [111-2123-M-259-002]
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Two series of hyper-coordinated halide-centered M-12 cuboctahedral clusters have been synthesized and characterized. The study reveals that the inverse coordination of halides significantly influences the size of the cuboctahedral M-12 framework.
Two series of hyper-coordinated halide-centered M-12 cuboctahedral clusters, [M-12(mu(12)-X){S2P((OPr)-Pr-n)(2)}(6){C 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 M-12 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 M-12 framework.
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