近日，中国科学院福建物质结构研究所陈忠宁团队研究了六齿配体锰（II）螯合物的高效电致变色金属聚合物薄膜。该项研究成果发表在2025年12月22日出版的《德国应用化学》杂志上。

为实现高性能电致变色，最关键的挑战之一在于如何获得透明态。

研究组精心设计了一种由三苯胺基团功能化的二乙烯三胺衍生六齿氮螯合剂，其与锰(II)离子配位形成八面体锰(II)螯合物。由于半充满d5轨道的锰(II)中心禁阻d-d电子跃迁，该锰(II)螯合物呈无色状态。通过对三苯胺基团进行电聚合，成功制备了以锰(II)螯合物为重复单元的透明金属聚合物薄膜。

在外加电压下，初始透明的金属聚合物薄膜中的锰(II)中心与三苯胺中心发生分步氧化，使无色薄膜在0.9 V电压下转变为棕黄色，并在1.3 V电压下进一步转变为蓝色。固态电致变色器件在1.7 V和2.4 V电压下分别实现从无色到棕黄色再到蓝色的三色电致变色。在无色与棕黄色态之间，着色/褪色时间、色对比度和电致变色效率分别为1.4秒/0.4秒、40%和337.5 cm² C^-1；而在无色与蓝色态之间，这些参数达到2.2秒/0.4秒、73%和397.1 cm² C^-1。该器件表现出优异的稳定性，锰基电致变色循环次数可达10,000次。

附：英文原文

Title: Metallopolymer Films of a Manganese(II) Chelate with Hexadentate Ligand for High-Performance Electrochromism

Author: Meng-Die Li, Li-Yi Zhang, Jin-Yun Wang, Jing-Yu Han, Xiang-Ying Qian, Xiao-Liang Ye, Feng-Rong Dai, Zhong-Ning Chen

Issue&Volume: 2025-12-22

Abstract: To achieve high-performance electrochromism, one of the most critical challenge is how to attain a transparent state. For this purpose, we elaborately designed a diethylenetriamine-derived hexadentate nitrogen chelator functionalized with triphenylamine groups, which coordinates with manganese(II) ion to form an octahedral manganese(II) chelate. As d–d transition of the half-filled d5 manganese(II) center is forbidden, this manganese(II) chelate is colorless. Through electropolymerization of triphenylamine groups, we successfully fabricated a transparent metallopolymer film with manganese(II) chelates as repeating units. Under applied potentials, the initially transparent metallopolymer film undergoes stepwise oxidation at both manganese(II) and triphenylamine centers, so that the colorless film turns brown-yellow at 0.9 V and further blue at 1.3 V. The solid-state electrochromic device exhibits tricolor electrochromism from colorless to brownish yellow and blue at the voltages of 1.7 and 2.4 V, respectively. The coloring/bleaching time, color contrast, and electrochromic efficiency are 1.4 s/0.4 s, 40%, and 337.5 cm2 C1 between colorless and brownish yellow, whereas they become 2.2 s/0.4 s, 73%, and 397.1 cm2 C1 between colorless and blue. The device exhibits excellent stability with up to 10 000 cycles for manganese-based electrochromism.

DOI: 10.1002/anie.202525500

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202525500