Multinary clusters comprising main group metal atoms and one or two further components – further (semi)metal atoms and/or chalcogen atoms and/or organic substituents – have attracted interest in recent times, owing to a number of uncommon properties. The most obvious feature is a large variety of different cluster compositions and architectures, but the materials do also show unexpected functionalities. Depending on the elemental composition, the clusters either belong to so-called intermetalloid clusters [Mx@E13/14yE15z]q– (E13/14 = Ga...Tl or Ge...Pb; E15 = P...Bi), hence comprising (semi)metal atoms in negative oxidation states, or they form chalcogenidometalate architectures of the general type [Mx(RE14)yE16z]q– (M = (transition) metal) with or without functional organic ligands R. While unsubstituted multinary clusters like [Ta@Ge6As4], [K2Zn20Bi16]6−, or [Th@Bi12]3–, serve to study structural variations and to gain new insights into cluster formation and bonding, organic substituents on the cluster surfaces, as in [Mn4Sn4Se13(SeMe)4]6–, shed light on reactivities. Moreover, they may also cause extreme non-linear optical properties that allow for the conversion of infrared light from an inexpensive CW laser diode into a directed white-light emission, rendering compounds like [(RT)4E6] (R = phenyl, styryl, cyclohexyl; Si, Ge, Sn; E = S, Se) potentially useful, innovative materials.

Multinary clusters as molecular platforms for energy conversion

ACS Spring 2022

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