Core-dependent properties of copper nanoclusters: valence-pure nanoclusters as NIR TADF emitters and mixed-valence ones as semiconductors.

We report herein that copper alkynyl nanoclusters show metal-core dependent properties a charge-transfer mechanism, which enables new understanding of their structure-property relationship. Initially, nanoclusters and bearing respective Cu(i) () and Cu(i) () cores were prepared and revealed to display near-infrared (NIR) photoluminescence mainly from the mixed alkynyl → Cu(i) ligand-to-metal charge transfer (LMCT) and cluster-centered transition, and they further exhibit thermally activated delayed fluorescence (TADF). Subsequently, a vanadate-induced oxidative approach to generate a nucleating Cu(ii) cation led to assembly of and featuring respective [Cu(ii)O]@Cu(i) () and {[Cu(ii)O]·[VO]}@Cu(i) () cores.

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

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.

Silver Thiolate Nano-sized Molecular Clusters and Their Supramolecular Covalent Frameworks: An Approach Toward Pre-templated Synthesis.

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.