Shott Jessica L, Freeman Matthew B, Saleh Nemah-Allah, Jones Daniel S, Paley Daniel W, Bejger Christopher
Department of Chemistry, The University of North Carolina at Charlotte , 9201 University City Boulevard, Charlotte, North Carolina 28223, United States.
Inorg Chem. 2017 Sep 18;56(18):10984-10990. doi: 10.1021/acs.inorgchem.7b01259. Epub 2017 Aug 28.
The superlattice structures of hierarchical cluster solids are dictated by short-range interactions between constituent building blocks. Here we show that shape complementary sites, as well as halogen and chalcogen bonding between exposed capping ligands and fullerides, govern the packing arrangement of the resulting binary solids. Four new superatomic solids, Ni(μ-I)(μ-dppm) (1·C), Ni(μ-I)(μ-dppm) (1·C), Ni(μ-Te)(μ-dppm) (2·C), and Ni(μ-Te)(μdppm) (2·C), (dppm = PhPCHPPh) were prepared and crystallized from solution. All four compounds were characterized by single crystal X-ray diffraction, IR spectroscopy, and SQUID magnetometry. Charge transfer between the molecular clusters is confirmed via optical spectroscopy and structural data. Compounds 1·C and 2·C are paramagnetic and 100 times more conductive than the constituent cluster precursors. The obtained solids exhibit close contacts, indicative of halogen/chalcogen bonds, between the fulleride anions and the nickel cluster capping ligands (I/Te) in the solid-state.
分级簇状固体的超晶格结构由构成结构单元之间的短程相互作用决定。在此我们表明，形状互补位点以及暴露的封端配体与富勒化物之间的卤素和硫族元素键，决定了所得二元固体的堆积排列。制备了四种新的超原子固体，即Ni(μ-I)(μ-dppm) (1·C)、Ni(μ-I)(μ-dppm) (1·C)、Ni(μ-Te)(μ-dppm) (2·C) 和 Ni(μ-Te)(μ-dppm) (2·C)，（dppm = PhPCHPPh），并从溶液中结晶出来。通过单晶X射线衍射、红外光谱和超导量子干涉仪磁力测定法对这四种化合物进行了表征。通过光谱学和结构数据证实了分子簇之间的电荷转移。化合物1·C和2·C是顺磁性的，导电性比组成簇前驱体高100倍。所得固体在固态下的富勒化物阴离子与镍簇封端配体（I/Te）之间呈现紧密接触，这表明存在卤素/硫族元素键。
