Temperature‐Mediated Template Release: Facile Growth of Copper(I) Mixed Ethynediide/Isopropylethynide Nanoclusters

Abstract

In the comproportionation reaction of CuIIX2 and Cu0 with isopropylacetylene (iPr−C≡C−H), the ethynediide species C22− is generated via concomitant C−H/C−C bond cleavage of the iPr−C≡C−H precursor under moderate temperature to direct the formation of CuI mixed ethynediide/isopropylethynide nanoclusters (potentially explosive). The active ethynediide dianion C22− exhibits chameleon‐like templating behavior to form C2@Cum (m=6 (3, 4), 7 (2, 4), 8 (1)) central structural units for successive formation of {C22−⊂Cu24} (1, 2), {6 C22−⊂Cu48} (3), and {18 C22−⊂Cu92} (4) complexes. Bearing the highest C22− content, complex 4 features an unprecedented nanoscale Cu2C2 kernel. Furthermore, 1–3 exhibit structure‐controlled photoluminescence in the solid state.