Blue Emitting Single Crystalline Assembly of Metal Halide Clusters

The rich chemistry of organic–inorganic metal halide hybrids has enabled the development of a variety of crystalline structures with controlled morphological and molecular dimensionalities. Here we report for the first time a single crystalline assembly of metal halide clusters, (C9NH20)7(PbCl4)­Pb3Cl11, in which lead chloride tetrahedrons (PbCl42–) and face-sharing lead chloride trimer clusters (Pb3Cl115–) cocrystallize with organic cations (C9NH20+) to form a periodical zero-dimensional (0D) structure at the molecular level. Blue light emission peaked at 470 nm with a photoluminescence quantum efficiency (PLQE) of around 83% was realized for this single crystalline hybrid material, which is attributed to the individual lead chloride clusters. Our discovery of single crystalline assembly of metal halide clusters paves a new path to functional cluster assemblies with highly tunable structures and remarkable properties.有机-无机金属卤化物杂化材料丰富的化学特性，已推动开发出一系列可精准调控形貌与分子维度的晶体结构。本研究首次报道了金属卤化物团簇的单晶组装体(C9NH20)7(PbCl4)­Pb3Cl11，其中氯化铅四面体(PbCl42–)与面共享型氯化铅三聚体团簇(Pb3Cl115–)与有机阳离子(C9NH20+)共结晶，在分子尺度上形成周期性零维(0D)结构。该单晶杂化材料实现了峰值位于470 nm的蓝光发射，光致发光量子效率(photoluminescence quantum efficiency, PLQE)约为83%，其发光特性源于单个氯化铅团簇。本研究发现的金属卤化物团簇单晶组装体，为构建结构高度可调、性能优异的功能性团簇组装体开辟了全新途径。