While valence-pure copper alkynyl nanoclusters show near-infrared TADF, the mixed-valence ones exhibit semiconductivity.

In the comproportionation reaction of Cu X and Cu with isopropylacetylene (iPr-C≡C-H), the ethynediide species C 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 Cu mixed ethynediide/isopropylethynide nanoclusters (potentially explosive). The active ethynediide dianion C exhibits chameleon-like templating behavior to form C @Cu (m=6 (3, 4), 7 (2, 4), 8 (1)) central structural units for successive formation of {C ⊂Cu } (1, 2), {6 C ⊂Cu } (3), and {18 C ⊂Cu } (4) complexes. Bearing the highest C content, complex 4 features an unprecedented nanoscale Cu C kernel. Furthermore, 1-3 exhibit structure-controlled photoluminescence in the solid state.

A series of seven new complexes including silver-thiolate molecular clusters and their covalent supramolecular frameworks have been assembled from the silver carbide precursor Ag C using a C pre-templated approach. Herein, two prototype clusters Ag (SR) and CO @Ag (SR) (R=isopropyl, cyclohexyl or tert-butyl; m=18 or 20) are employed to construct cluster-based metal-organic frameworks of different dimensions. In particular, both new ellipsoidal tetradecanuclear molecular cluster compounds, namely, Ag (S-iPr) (CO CF ) ⋅(DMSO) (two polymorphic forms 1, 2) and [Ag (S-Cy) (CO CF ) (DMSO) ]⋅(DMSO) (3), and a cluster-based metal-organic framework {Ag [Ag (S-iPr) (CO CF ) (H O) CH OH]⋅(H O) } (4) have been isolated and structurally characterized. Furthermore, increased acidity of the reaction mixture afforded three carboxylate-templated cluster based frameworks: a chain-like compound {[HN(CH ) CO]⋅[CO @Ag (S-tBu) (NO ) (DMF) ]⋅DMF} (5), as well as two layer-type compounds, namely, {Ag[CO @Ag (S-iPr) (CO CF ) (CO HCF )(CH OH) ]} (6) and {Ag [CO @Ag (S-Cy) (CO CF ) (CO HCF ) (H O) ]⋅(H O) ⋅(CH OH) } (7) exhibiting sql-net characteristics. It is demonstrated that the C≡C pre-template, which draws several Ag ions together to form the C @Ag entity, plays an indispensable role in the syntheses of these compounds. Furthermore, covalent linkage of these nano-sized silver thiolate clusters from one- to three-dimensions revealed enormous potential for the future development of silver cluster-based frameworks.

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.