吉林大学陈龙团队报道了高结晶2D导电金属有机框架的从头设计和简单合成。相关研究成果于2024年3月20日发表于国际顶尖学术期刊《美国化学会杂志》。

二维导电金属-有机框架（2D c-MOFs）具有高电导率和大载流子迁移率的特点，在电子和光电子领域具有巨大的前景。然而，常用平面配体的有限溶解度不可避免地给合成和纯化带来挑战，并导致筛选的配位条件困难。此外，大多数报道的2D c-MOFs是结晶度相对较低、形态不规则的多晶粉末，阻碍了详细结构-功能关系的揭示。

该文中，研究人员开发了一种“转子-定子”分子设计策略，使用精心设计的非平面双咔唑配体（8OH-DCB）构建2D c-MOFs。得益于配体的特殊“转子-定子”结构，成功地制备了Cu-DCB-MOF的晶体，从而能够精确测定其晶体结构。有趣的是，Cu-DCB-MOF晶体可以在各种有机溶剂中获得，表明其具有良好的溶剂相容性。另外两种具有“转子-定子”结构的新配体进一步证明了“转子-转子”分子设计策略的多功能性，并提供了相应的2D c-MOF晶体（Cu-DCBT-MOF和Cu-DCBB-MOF）。

目前的工作提供了一种使用非平面配体，合理设计和直接构建高结晶2D c-MOFs的简单方法。

附：英文原文

Title: De Novo Design and Facile Synthesis of Highly Crystalline 2D Conductive Metal–Organic Frameworks: A “Rotor-Stator” Strategy

Author: Xi Su, Zhiye Zhong, Xiaoli Yan, Yunpeng Xu, Ting Zhang, Yanhang Ma, Long Chen

Issue&Volume: March 20, 2024

Abstract: Two-dimensional conductive metal–organic frameworks (2D c-MOFs), which feature high electrical conductivity and large charge carrier mobility, hold great promise in electronics and optoelectronics. Nevertheless, the limited solubility of commonly used planar ligands inevitably brings challenges in synthesis and purification and causes laborious coordination conditions for screening. Moreover, most reported 2D c-MOFs are polycrystalline powders with relatively low crystallinity and irregular morphology, hindering the unveiling of the detailed structure–function relationship. Herein, we developed a “rotor-stator” molecular design strategy to construct 2D c-MOFs using a delicately designed nonplanar biscarbazole ligand (8OH-DCB). Benefiting from the special “rotor-stator” structure of the ligand, crystals of Cu-DCB-MOF were successfully prepared, allowing for the precise determination of their crystal structure. Interestingly, the crystals of Cu-DCB-MOF can be obtained in various organic solvents, indicating excellent solvent compatibility. The versatility of the “rotor-stator” molecular design strategy was further demonstrated by another two new ligands with a “rotor-stator” structure, and afford corresponding 2D c-MOF crystals (Cu-DCBT-MOF and Cu-DCBBT-MOF). The current work presents a facile approach toward the rational design and direct construction of highly crystalline 2D c-MOFs using nonplanar ligands.

DOI: 10.1021/jacs.3c13985

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.3c13985