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

• Published in: Angewandte Chemie International Edition 2017-12, Vol.56 (51), p.16228-16232
• Main Authors: Zhang, Leon Li‐Min, Mak, Thomas C. W.
• Format: Article
• Language: English
• Subjects: carbon–carbon bond cleavage; cluster compounds; copper; ethynediide; Nanoclusters; Photoluminescence; Photons; Temperature; template synthesis
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201708760

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. Template release: Temperature variation triggers the release of ethynediide C22− from isopropylacetylene through concomitant C−H/C−C bond cleavage, leading to formation of CuI mixed ethynediide/alkynide nanoclusters. Synthesis of {C22−⊂Cu24}, {6 C22−⊂Cu48}, and {18 C22−⊂Cu92} establishes a class of tunable nanostructures where the increasing number of ethynediide bestows nuclearity expansion and structural diversity.