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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
Synthesis, structural studies, and photophysical properties of heteroleptic inverse-coordination clusters
Guan-Rong Huang1, Rhone P Brocha Silalahi1, Jian-Hong Liao1
1Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd, Shoufeng, Hualien 974301, Taiwan, Republic of China. chenwei@gms.ndhu.edu.tw.
Abstract:
Two series of hyper-coordinated halide-centered M12 cuboctahedral clusters, [M12(μ12-X){S2P(OPr)2}6{CCPh}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.
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