近日，北京大学窦锦虎团队研究了不对称取代操纵二维导电MOF晶体的堆叠模式。2025年12月17日出版的《美国化学会志》发表了这项成果。

二维导电金属-有机框架（2D c-MOFs）的堆叠模式作为关键设计参数，能够精确调控电荷传输路径，进而直接影响载流子迁移率及各向异性传输行为。然而，通过自下而上的合成方法精确调控具有原子级精度的二维c-MOF单晶结构堆叠模式，目前仍面临重大挑战。其根本原因在于二维c-MOF合成过程中配位键占据主导地位，而配体间的弱范德华相互作用往往被压制，难以在最终MOF结构中得以表达。此外，大多数二维c-MOF仅能以纳米晶粉末形式获得，这使得获取精确结构信息变得尤为困难。

研究组报道了一种通过配体非对称静电势调控实现二维c-MOF可控堆叠与结晶度提升的新策略。通过将氟原子策略性地取代至六羟基苯并菲（HHTP）配体中，他们调控了其本征电荷分布，成功合成了具有不同堆积模式的两种HHTP衍生物。基于此方法合成的c-MOF晶体展现出明显差异的堆叠模式与可调控的电学性能。该工作通过系统调控配体堆叠构型，阐明了二维c-MOF中基本的结构-性能关联规律，为定制具有优化性能特征的二维c-MOF材料提供了理性设计策略。

附：英文原文

Title: Asymmetrical Substitution Manipulates Stacking Modes in 2D Conductive MOF Crystals

Author: Yi Liu, Huiying Yao, Haoyang Zhang, Chao Ma, Jinkun Guo, Yunlong Fan, Hao Chen, Xinyan Wu, Luming Yang, Xing Huang, Tianyang Chen, Qingqing Ji, Ze-Fan Yao, Jian Li, Jin-Hu Dou

Issue&Volume: December 17, 2025

Abstract: The stacking modes in two-dimensional conductive metal–organic frameworks (2D c-MOFs) serve as a pivotal design parameter for precisely controlling charge transport pathways, thereby directly regulating carrier mobility and anisotropic transport. Precise control over the stacking modes of atomically precise single-crystal structures of 2D c-MOFs through the bottom-up synthesis remains a major challenge. The reason lies in the dominant role of coordination bonds during 2D c-MOF synthesis, where the weak van der Waals interactions between ligands are often overridden and fail to be expressed in the final MOF architecture. Moreover, most 2D c-MOFs can only be obtained as nanocrystalline powders, making it difficult to obtain precise structural information. Here, we report a new strategy for achieving controllable stacking and enhanced crystallinity in 2D c-MOFs through the asymmetrical electrostatic potential modulation of ligands. By strategically substituting fluorine atoms into the hexahydroxytriphenylene (HHTP) ligands, we modulated the intrinsic charge distribution, enabling the synthesis of two HHTP derivatives with different packing modes. The c-MOF crystals synthesized through this approach exhibit distinct stacking modes and tunable electrical properties. Through the systematic modulation of ligand stacking configurations, this work elucidates fundamental structure–property correlations in 2D c-MOFs, providing a rational design strategy for tailoring 2D c-MOF materials with optimized performance characteristics.

DOI: 10.1021/jacs.5c15827

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c15827