南京大学雷建平小组取得一项新突破。他们研制了单杂配体金属有机晶体的多色电化学发光成像。这一研究成果于2025年3月4日发表在国际顶尖学术期刊《德国应用化学》上。

传统的多色电化学发光（ECL）成像是利用不同电势下的几个独立发光团来实现的。本研究以单杂配体金属有机骨架（MOF）晶体为纳米发射体，通过网状能量传递过程构建了一种新兴的多色ECL成像系统。将中位四（4-羧基苯基）卟啉（TCPP）与1,3,6,8-四（对苯甲酸）芘（tbay）配体共组装，制备了具有配位能力的杂配体MOF晶体h-NJU-241，使两个配体之间的共轭间距为0.624 nm。值得注意的是，当TCPP受体与ttby供体配位质量比仅为1.87‰时，能量传递效率为92.2%。与单配体MOF不同，杂配体h-NJU-241在一步应用电位下表现出蓝色和红色区域的双ECL发射，这是单MOF晶体多色ECL成像的第一个例子。

此外，通过调整反应条件，可以动态控制卟啉在晶体内的形态分布，为多色ECL成像的解码基础提供定制的晶体平台。

附：英文原文

Title: Polychromatic Electrochemiluminescence Imaging of Single Hetero-Ligand Metal Organic Crystals

Author: Yufei Wang, Tianrui Liu, Siqi Yu, Rengan Luo, Songsong Bao, Jie Wu, Huangxian Ju, Zhihui Dai, Jianping Lei

Issue&Volume: 2025-03-04

Abstract: Conventional polychromatic electrochemiluminescence (ECL) imaging is realized with the several separated luminophores at the different potentials. In this study, an emerging polychromatic ECL imaging system was constructed based on single hetero-ligand metal organic framework (MOF) crystals as nanoemitters through an intrareticular energy transfer process. The hetero-ligand MOF crystals, named h-NJU-241, were co-assembled of meso-tetrakis(4-carboxyphenyl)porphyrin (TCPP) with 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy) ligand using benzoic acid catalyst with coordination ability, leading to the conjugated spacing of 0.624 nm between two ligands. Remarkably, an energy transfer efficiency of 92.2% was achieved when the coordination weight ratio of TCPP acceptor and TBAPy donor was only 1.87‰. Different from monoligand MOFs, the hetero-ligand h-NJU-241 exhibits dual ECL emissions in both blue and red regions at one step applied potential, which is first example of polychromatic ECL imaging for single MOF crystals. Furthermore, by adjusting the reaction conditions, the morphology distribution of porphyrin within the crystal can be dynamically controlled, providing a tailored crystal platform for decoding fundamentals in polychromatic ECL imaging.

DOI: 10.1002/anie.202501151

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202501151