Metal chalcogenide magic-sized nanoclusters have shown intriguing photophysical and chemical properties, yet ambient instability has hampered their extensive applications. Here we explore the periodic assembly of these nanoscale building blocks through organic linkers to overcome such limitations and further boost their properties. We designed a diamine-based heat-up self-assembly process to assemble Mn²⁺:(CdSe)₁₃ and Mn²⁺:(ZnSe)₁₃ magic-sized nanoclusters into three- and two-dimensional suprastructures, respectively, obtaining enhanced stability and solid-state photoluminescence quantum yields (from <1% for monoamine-based systems to ~72% for diamine-based suprastructures). We also exploited the atomic-level miscibility of Cd and Zn to synthesize Mn²⁺:(Cd_1−xZn_xSe)₁₃ alloy suprastructures with tunable metal synergy: Mn²⁺:(Cd_0.5Zn_0.5Se)₁₃ suprastructures demonstrated high catalytic activity (turnover number, 17,964 per cluster in 6 h; turnover frequency, 2,994 per cluster per hour) for converting CO₂ to organic cyclic carbonates under mild reaction conditions. The enhanced stability, photoluminescence and catalytic activity through combined cluster-assembly and metal synergy advance the usability of inorganic semiconductor nanoclusters.

金属硫族化物神奇大小的纳米团簇显示出有趣的光物理和化学性质，但环境不稳定性阻碍了它们的广泛应用。在这里，我们通过有机连接体探索这些纳米级构建块的周期性组装，以克服这些限制并进一步提高它们的性能。我们设计了一种基于二胺的加热自组装工艺来组装 Mn ²⁺ :(CdSe) ₁₃和 Mn ²⁺ :(ZnSe) ₁₃魔术尺寸的纳米团簇分别进入三维和二​​维超结构，获得增强的稳定性和固态光致发光量子产率（从基于单胺的系统的 <1% 到基于二胺的超结构的~72%）。我们还利用 Cd 和 Zn 的原子级混溶性来合成 Mn ²⁺ :(Cd _{1− x} Zn _x Se) ₁₃种具有可调金属协同作用的合金超结构：Mn ²⁺ :(Cd _0.5 Zn _0.5 Se) ₁₃种超结构表现出高转化 CO ₂的催化活性（周转数，6 小时内每个簇 17,964；周转频率，每个簇每小时 2,994）在温和的反应条件下生成有机环状碳酸酯。通过结合团簇组装和金属协同作用增强的稳定性、光致发光和催化活性提高了无机半导体纳米团簇的可用性。