Mechanochemical Construction of 0D Cu(I)-Based Luminescent Superclusters through Dynamic Ligand Fusion: Toward Eco-Friendly Stimuli-Switchable Optical Materials

作者：Zhenwei Guo, Daming Feng, Fang Guo · 发表于：Inorganic Chemistry · 年份：2025 · DOI：10.1021/acs.inorgchem.5c02543 · 被引用次数：7 · 研究领域：Luminescence and Fluorescent Materials、Nanoplatforms for cancer theranostics、Nanocluster Synthesis and Applications

Zero-dimensional (0D) Cu(I)-based organic–inorganic metal halides (OIMHs) show promise for optoelectronics but face challenges in eco-friendly synthesis and stability. We present a solvent-free mechanochemical strategy to construct luminescent multinuclear clusters via a dynamic ligand fusion. Starting from the preorganized dinuclear complex (BPBI) 2 Cu 2 Br 4 ( BPBI = 1-benzyl-3-(2-pyridinylmethyl)-1 H -benzoimidazol-3-ium), the in situ formation of cationic [6,5,5,6]-fused heterotetracyclic ligands is driven by the Cu(I)-mediated C–N coupling between imidazole carbene and pyridine groups under alkali-driven mechanochemical conditions ( t -BuONa). This process is supposed to involve a N -heterocyclic carbene-copper intermediate that directs the assembly toward the 0D organic–inorganic multinuclear cluster (BBIIP) 4 Cu 4 Br 8 ( BBIIP = 6-benzyl-6H-benzo[4′,5′]imidazo[2′,1′:2,3]-imidazo[1,5- a ]pyridin-11-ium), where the planar π-conjugated BBIIP + cationic coordinate with the [Cu 4 Br 8 ] 4– cluster to strengthen Cu···Cu interactions and stabilize the lattice. Crystallographic and DFT analyses demonstrate that the cluster’s rigid architecture contributes to its photophysical performance: a photoluminescence quantum yield of 93%, lifetime of 6.01 μs, and thermal stability up to 300 °C. Furthermore, the ligand–cation interactions enable stimuli-responsive dual-mode emissions, with reversible spectral shifts and intensity modulation upon thermal and solvent stimuli, a behavior r...