This review summarizes recent advances in silver nanoclusters focusing on their controlled synthesis, crystal structures and photoluminescence.

Two‐dimensional (2D) graphitic carbon nitride (g‐CN) is a promising anode material for sodium‐ion batteries (SIBs), but its insufficient interlayer spacing and poor electronic conductivity impede its sodium storage capacity and cycling stability. Herein, we report the fabrication of a fullerene (C60)‐modified graphitic carbon nitride (C60@CN) material which as an anode material for SIBs shows a high‐reversible capacity (430.5 mA h g−1 at 0.05 A g−1, about 3 times higher than that of pristine g‐CN), excellent rate capability (226.6 mA h g−1 at 1 A g−1) and ultra‐long cycle life (101.2 mA h g−1 after 5000 cycles at 5 A g−1). Even at a high‐active mass loading of 3.7 mg cm−2, a reversible capacity of 316.3 mA h g−1 can be obtained after 100 cycles. Such outstanding performance of C60@CN is attributed to the C60 molecules distributed in the g‐CN nanosheets, which enhance the electronic conductivity and prevent g‐CN sheets from restacking, thus resulting in enlarged interlayer spacing and exposed edge N defects (pyridinic N and pyrrolic N) for sodium‐ion storage. Furthermore, a sodium‐ion full cell combining C60@CN anode and NVPF@rGO cathode provides high‐coulombic efficiency (>96.5%), exceptionally high‐energy density (359.8 W h kganode−1 at power density of 105.1 W kganode−1) and excellent cycling stability (89.2% capacity retention over 500 cycles at 1 A ganode−1). This work brings new insights into the field of carbon‐based anode materials for SIBs.

Reaction of AgCC t Bu with (EtO)2PS2Na at room temperature leads to the isolation of two new silver­(I)-ethynide compounds incorporating the dithiophosphate ligand, namely, {CO3@(Ag3)4(CC t Bu)4(EtO)2PS2]6}·0.5H2O (1) and {(CO3)2@Ag26(CC t Bu)16[(EtO)2PS2]4}·2­(OH)·4MeOH·6H2O (2). Besides, we obtain another three silver­(I)-ethynide clusters S@Ag11(CC t Bu)2[(EtO)2PS2]7 (3), {S@Ag14(CCPh)8[(EtO)2PS2]4(TMEDA)2}·5MeOH (4), and {S@Ag14(CCPh)8[( i PrO)2PS2]4(TMEDA)2}·7CH3OH (5), with AgCCR (R= t Bu, Ph) and (RO)2PS2Na (R= Et, i Pr) as the starting materials. Complexes 1–2 are templated by a carbonate anion in situ generated from the fixation of atmospheric CO2 in a basic TMEDA-containing solution, and TMEDA can also lead to the disassembly of dithiophosphate to give a sulfide ion as the template for the generation of 3–5.

Phosphonate can act as the intermediate connector to link two silver ethynide clusters functionalized by hfac ligands together to enlarge the silver cluster.

Four copper­(I) alkynyl complexes incorporating phosphate ligands, namely, [Cu16( t BuCC)12(PhOPO3)2] n (1; PhOPO3 = phenyl phosphate), [Cu16( t BuCC)12(1-NaphOPO3)2] n (2; 1-NaphOPO3 = 1-naphthyl phosphate), [VO4@Cu25( t BuCC)19(1-NaphOPO3)]­(PF6)0.5(F)0.5 (3), and [PO4@Cu25( t BuCC)19(1-NaphOPO3)]­(PF6)0.5(F)0.5 (4), were solvothermally synthesized and well-characterized by IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystal X-ray analysis revealed that the Cu16 cluster-based coordination chain polymers 1 and 2 are formed by assembly during crystallization, while 3 and 4 contain high-nuclearity copper­(I) composite clusters enclosing orthovanadate and phosphate template ions, respectively, that are supported by ROPO3 2– ligands. Complexes 1–4 exhibit crystallization-induced emission enhancement. Their crystalline state shows strong luminescence, in striking contrast to the weak emission of the amorphous state and solution phase. A detailed investigation of the crystal structure suggests that well-arranged C–H···π and π···π interactions between the ligands are the major factors for this enhanced emission. Clusters 3 and 4 also exhibit photocurrent responses upon visible-light illumination.