近日，美国加州大学伯克利分校杨培东院士团队报道了分子线交替冠醚和金属卤化物配合物的超分子组装。相关论文于2026年3月30日发表在《自然-化学》杂志上。

金属-卤化物配合物是卤化物钙钛矿中的关键发光中心，然而通过自下而上的组装策略精确调控其空间排布仍面临挑战。

研究组展示了一种冠醚辅助的超分子组装策略，能够将金属-卤化物配合物与（冠醚@A）²⁺配合物（其中A为碱土金属阳离子）交替连接成一维分子线，进而堆积成六方晶体结构。这一过程成功制备出具有绿色发射的(18C6@Ba)MnBr₄单晶，其光致发光量子产率超过80%，半峰宽较窄。此外，该非中心对称晶体结构还产生了强的非线性光学响应，包括二次谐波产生。

这种通用的超分子组装方法可推广用于构建多种[M(I)X₂]^-、[M(I)X₃]^2-、[M(II)X₄]^2-和[M(III)X₅]^2-分子线，为拓展不同发光颜色和独特光学性质提供了广阔前景。该策略为构建具有多样光学功能的超分子金属-卤化物构筑基元提供了通用设计原则。

附：英文原文

Title: Supramolecular assembly of molecular wires alternating crown ethers and metal–halide complexes

Author: Zhu, Heqing, Zhu, Cheng, Le, Han K. D., Chabeda, Daniel, Field, Bernard, Wen, Chuxi, Oddo, Alexander M., Jiang, Yuxin, Jayasinghe, Lihini, Shan, Yu, Verbitsky, Lior, Jayakumar, Harishankar, Griffin, Sinad M., Rabani, Eran, Yang, Peidong

Issue&Volume: 2026-03-30

Abstract: Metal–halide complexes serve as key emissive centres in halide perovskites; however, precise control over their spatial organization through bottom-up assembly is challenging. Here we show that a crown-ether-assisted supramolecular assembly strategy can alternatingly connect metal–halide complexes and (crown ether@A)2+ (where ‘A’ is an alkaline earth metal cation) complexes into a one-dimensional molecular wire, which can then be packed into a hexagonal crystal structure. This process resulted in the creation of an (18C6@Ba)MnBr4 single crystal with green emission, achieving over 80% photoluminescence quantum yield and a narrow full width at half maximum. In addition, the non-centrosymmetric crystal structure gave rise to strong nonlinear optical responses, including second-harmonic generation. This versatile supramolecular assembly approach could be generalized to create various [M(I)X2], [M(I)X3]2, [M(II)X4]2 and [M(III)X5]2 molecular wires, broadening the potential for diverse emission colours and distinct optical properties. This strategy provides a general design principle for constructing supramolecular metal–halide building blocks with diverse optical functionalities.

DOI: 10.1038/s41557-026-02101-0

Source: https://www.nature.com/articles/s41557-026-02101-0