Tuning the Electronic Structure of Atomically Precise Sn/Co/Se Nanoclusters via Redox Matching of Tin(IV) Surface Sites

A new strategy is reported to tailor the electronic properties of a superatomic metal chalcogenide cluster by redox matching the cluster core with surface tin(IV) sites. Two ternary clusters (SnR2)(3)Co6Se8L6 (R = Me, Bu-n) are synthesized by salt metathesis from the hexalithiated salt [Li-2(py)(2)](3)Co6Se8L6 and R2SnCl2. Cyclic and differential-pulse voltammetry studies reveal that the tristannylated clusters feature two new, near-degenerate, electronic states within the highest occupied molecular orbital-lowest unoccupied molecular orbital gap of the Co6Se8 core, which are attributed to the reduction of a surface tin site. Single-crystal X-ray diffraction analysis reveals that no Sn center dot center dot center dot Se coordination is present in the solid state. The single-crystal X-ray structure of the hexalithiated salt starting material is reported for the tetrahydrofuran (THF) adduct variant [Li-2(THF)(2)](6)Co6Se8L6.

Automated summary

A new strategy was reported to tailor the electronic properties of a superatomic metal chalcogenide cluster by redox matching the core with surface tin(IV) sites. Two ternary clusters were synthesized using salt metathesis, showing new electronic states attributed to the reduction of a surface tin site. X-ray diffraction analysis revealed no Sn···Se coordination in the solid state.