Le Phuong H, Liu Andong, Zasada Leo B, Geary Jackson, Kamin Ashlyn A, Rollins Devin S, Nguyen Hao A, Hill Audrey M, Liu Yayuan, Xiao Dianne J
Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, United States.
Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, Maryland 21218, United States.
Angew Chem Int Ed Engl. 2025 Mar 10;64(11):e202421822. doi: 10.1002/anie.202421822. Epub 2024 Dec 16.
Here we report a series of nitrogen-rich conjugated macrocycles that mimic the structure and function of semiconducting 2D metal-organic and covalent organic frameworks while providing greater solution processability and surface tunability. Using a new tetraaminotriphenylene building block that is compatible with both coordination chemistry and dynamic covalent chemistry reactions, we have synthesized two distinct macrocyclic cores containing Ni-N and phenazine-based linkages, respectively. The fully conjugated macrocycle cores support strong interlayer stacking and accessible nanochannels. For the metal-organic macrocycles, good out-of-plane charge transport is preserved, with pressed pellet conductivities of 10 S/cm for the nickel variants. Finally, using electrochemically mediated CO capture as an example, we illustrate how colloidal phenazine-based organic macrocycles improve electrical contact and active site electrochemical accessibility relative to bulk covalent organic framework powders. Together, these results highlight how simple macrocycles can enable new synthetic directions as well as new applications by combining the properties of crystalline porous frameworks, the processability of nanomaterials, and the precision of molecular synthesis.
在此，我们报道了一系列富氮共轭大环化合物，它们模仿二维半导体金属有机和共价有机框架的结构与功能，同时具有更高的溶液可加工性和表面可调性。使用一种新型的四氨基三苯基苯构建块，其与配位化学和动态共价化学反应均兼容，我们分别合成了两个不同的大环核心，一个含有镍氮键，另一个含有吩嗪基连接键。完全共轭的大环核心支持强层间堆积和可及的纳米通道。对于金属有机大环化合物，面外电荷传输性能良好，镍变体的压制片电导率为10 S/cm。最后，以电化学介导的二氧化碳捕获为例，我们说明了相对于本体共价有机框架粉末，基于吩嗪的胶体有机大环化合物如何改善电接触和活性位点的电化学可及性。总之，这些结果突出了简单的大环化合物如何通过结合结晶多孔框架的性质、纳米材料的可加工性和分子合成的精确性，开辟新的合成方向以及新的应用。
