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Ball and Socket Assembly of Binary Superatomic Solids Containing Trinuclear Nickel Cluster Cations and Fulleride Anions
No full textThe 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<sub>3</sub>(μ<sub>3</sub>-I)<sub>2</sub>(μ<sub>2</sub>-dppm)<sub>3</sub><sup>+</sup>]Â(C<sub>60</sub><sup>•‑</sup>) (<b>1·</b>C<sub>60</sub>), [Ni<sub>3</sub>(μ<sub>3</sub>-I)<sub>2</sub>(μ<sub>2</sub>-dppm)<sub>3</sub><sup>+</sup>]Â(C<sub>70</sub><sup>–</sup>)<sub>2</sub> (<b>1·</b>C<sub>70</sub>), [Ni<sub>3</sub>(μ<sub>3</sub>-Te)<sub>2</sub>(μ<sub>2</sub>-dppm)<sub>3</sub><sup>+</sup>]Â(C<sub>60</sub><sup>•‑</sup>) (<b>2·</b>C<sub>60</sub>),
and [Ni<sub>3</sub>(μ<sub>3</sub>-Te)<sub>2</sub>(μ<sub>2‑</sub>dppm)<sub>3</sub>]Â(C<sub>70</sub><sup>–</sup>)<sub>2</sub> (<b>2·</b>C<sub>70</sub>), (dppm = Ph<sub>2</sub>PCH<sub>2</sub>PPh<sub>2</sub>) 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 <b>1·</b>C<sub>60</sub> and <b>2·</b>C<sub>60</sub> 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
