Ball and Socket Assembly of Binary Superatomic Solids Containing Trinuclear Nickel Cluster Cations and Fulleride Anions.

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, [Ni3 (μ3 -I)2 (μ2 -dppm)3 + ](C60 •- ) (1·C60 ), [Ni3 (μ3 -I)2 (μ2 -dppm)3 + ](C70 - )2 (1·C70 ), [Ni3 (μ3 -Te)2 (μ2 -dppm)3 + ](C60 •- ) (2·C60 ), and [Ni3 (μ3 -Te)2 (μ2- dppm)3 ](C70 - )2 (2·C70 ), (dppm = Ph2 PCH2 PPh2 ) 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·C60 and 2·C60 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.