中国科学院大连化学物理研究所吴凯丰团队实现了聚合金属卤化物的多阳离子工程使单一过渡金属可调多色发射。这一研究成果发表在2025年7月8日出版的《德国应用化学》杂志上。

零维金属卤化物已经成为开发发光材料的多功能平台，但从含有单一类型金属的材料中实现可调甚至多色发射已被证明极具挑战性。研究组利用最近开发的聚合物金属卤化物的“结构容差”将单一金属的两个不同配位单元整合到材料中，从而在单相金属卤化物中实现高度可调的光学性能。通过操纵聚阳离子的空间位阻，可以在溴化锰中实现易于调节的绿色、红色或双色发射，这源于溴化锰四面体向八面体的可控转化。 

该设计原理进一步扩展到聚合物卤化铜，其中通过调整成分、激发波长或温度，来自不同铜碘多面体的宽自陷激子发射允许发射颜色从蓝色到黄色线性可调，包括纯白光。该研究通过利用金属元素的内在配位多样性，为金属卤化物光学性质的简单和精确调制开辟了途径。

附：英文原文

Title: Polycation Engineering in Polymeric Metal Halides Enables Tunable and Multicolor Emission from Single Transition-Metals

Author: Shun-Shun Li, Pengfei Cheng, Huaxin Liu, Juntao Li, Jianyong Liu, Junsheng Chen, Kaifeng Wu

Issue&Volume: 2025-07-08

Abstract: Zero-dimensional metal halides have emerged a versatile platform for the development of light-emitting materials, but achieving tunable or even multicolor emission from a material containing a single type of metal has proven highly challenging. Here, we leverage the “structural tolerance” of recently-developed polymeric metal halides to integrate two distinct coordination units of a single metal into a material, thereby achieving highly tunable optical properties in single-phase metal halides. By manipulating the steric hindrance of polycations, facilely adjustable green, red or bicolor emission can be realized in manganese bromides, which originates from controllable transformation from manganese-bromine tetrahedra into octahedra. This design principle is further extended to polymeric copper halides, wherein broad self-trapped exciton emissions derived from distinct copper-iodine polyhedrons allow the emission colors to be linearly tunable from blue to yellow, encompassing pure white light, by tailoring the composition, excitation wavelength, or temperature. This study opens avenues for facile and precise modulation of the optical properties of metal halides by exploiting the intrinsic coordinative diversity of metal elements.

DOI: 10.1002/anie.202502210

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202502210