近日，南方科技大学权泽卫团队实现了通过压力聚合制备低维杂化卤化铅。该研究于2025年12月8日发表在《美国化学会志》上。

压力是调节杂化金属卤化物（HMHs）的有力工具，但减压后其效果往往相反。

使用不饱和间氨基苯基乙炔（m-APA）阳离子，研究组报道了压力诱导聚合（PIP）作为三种异质结构HMH晶体的不可逆带结构工程策略：（m-APA）₂Pb₃I₈，(m-APA)₂PbBr₄和（m-APA）PbCl₃。不同的聚合途径产生新的环境稳定相窄带隙和重新配置的带对齐。所得到的聚合物阳离子表现出不同的sp²/sp³-C比率，这显著地调节了有机-无机界面上的电子耦合。

具体来说，P-(m-APA)₂Pb₃I₈在无机亚晶格化学压力的驱动下保持了I型排列，而P-(m-APA)₂PbBr₄经历了I型到II型的转变，P-(m-APA)PbCl₃通过有机带边重建从II型转变为反转的I型。这项工作证明了PIP是一种新颖而通用的方法，可以永久地定制HMHs的电子结构，通过在高压下控制有机阳离子的共价转化来实现功能设计。

附：英文原文

Title: Sculpting Low-Dimensional Hybrid Lead Halides via Pressure-Induced Polymerization

Author: Xiaofan Xu, Peijie Zhang, Jiang Han, Yawen Li, Jie Liu, Yunfan Fei, Jinlong Zhu, Haiyan Zheng, Zewei Quan

Issue&Volume: December 8, 2025

Abstract: Pressure is a powerful tool to modulate hybrid metal halides (HMHs), but its effects are often reversed upon decompression. Here, using the unsaturated m-aminophenylacetylene (m-APA) cation, we report pressure-induced polymerization (PIP) as a strategy for irreversible band-structure engineering in three heterostructures as HMH crystals: (m-APA)2Pb3I8, (m-APA)2PbBr4, and (m-APA)PbCl3. Distinct polymerization pathways yield novel ambient-stable phases with narrowed band gaps and reconfigured band alignments. The resulting polymeric cations exhibit varied sp2/sp3-C ratios, which significantly tune the electronic coupling across organic–inorganic interfaces. Specifically, P-(m-APA)2Pb3I8 retains type I alignment with gap narrowing driven by chemical pressure on the inorganic sublattice, while P-(m-APA)2PbBr4 undergoes a type I to type II transition, and P-(m-APA)PbCl3 transforms from type II to reversed-type I via organic band-edge reconstruction. This work demonstrates PIP as a novel and general approach to permanently tailor the electronic structures of HMHs, enabling functional design through the controlled covalent transformation of organic cations under high pressure.

DOI: 10.1021/jacs.5c16046

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c16046