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

• Published in: Dalton transactions : an international journal of inorganic chemistry 2022-10, Vol.51 (41), p.1593-15911
• Main Authors: Huang, Guan-Rong, Silalahi, Rhone P. Brocha, Liao, Jian-Hong, Chiu, Tzu-Hao, Liu, C. W
• Format: Article
• Language: English
• Subjects: Clusters; Coordination; Copper; Crystal structure; Crystallography; Halides; Infrared spectroscopy; NMR spectroscopy; Photoluminescence; Silver; Single crystals; Structural analysis
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d2dt02100e

Two series of hyper-coordinated halide-centered M 12 cuboctahedral clusters, [M 12 (μ 12 -X){S 2 P(O n Pr) 2 } 6 {C&z.tbd;CPh} 4 ](PF 6 ), 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. By considering all 24 adjacent M M distances of the cuboctahedral framework, substitution of an inverse coordination halide (Cl, Br, and I) has influenced the size of the cuboctahedral M 12 framework.