Lu Chenwei, Choi Ji Yong, Check Brianna, Fang Xiaoyu, Spotts Samuel, Nuñez Dario, Park Jihye
Department of Chemistry, University of Colorado Boulder, Boulder, Colorado 80309, United States.
J Am Chem Soc. 2024 Sep 25;146(38):26313-26319. doi: 10.1021/jacs.4c08659. Epub 2024 Sep 16.
Functionalizing the organic building blocks of electrically conductive MOFs (EC-MOFs) can be a powerful method for adjusting the electronic structure and introducing a specific chemistry. However, designing EC-MOF linkers with reactive functional groups for postsynthetic modification is challenging due to the requirements of d-p conjugation. This work addresses such design limitations by synthesizing an EC-MOF, Cu-thiatruxene (Cu-thiaTRX). This conductive framework incorporated a truxene-based linker with heterocyclic sulfur, allowing for efficient conjugation and an electrical conductivity of 2.2 × 10 S cm. Harnessing sulfur chemistry in Cu-thiaTRX involves a two-step postsynthetic modification: oxidation and SAr. The sulfinic groups introduced in the framework enabled tunable proton conductivity, leading to a 200-fold improvement. These results highlight the importance of a rational linker design for functionalization.
功能化导电金属有机框架（EC-MOFs）的有机结构单元是调整电子结构和引入特定化学性质的有效方法。然而，由于d-p共轭的要求，设计具有用于后合成修饰的反应性官能团的EC-MOF连接体具有挑战性。这项工作通过合成一种EC-MOF，即铜-噻吨并三苯（Cu-thiaTRX）来解决此类设计限制。这种导电框架包含一个带有杂环硫的三苯并三苯连接体，实现了高效共轭，电导率为2.2×10 S cm。利用Cu-thiaTRX中的硫化学涉及两步后合成修饰：氧化和SAr。框架中引入的亚磺酰基实现了可调质子传导率，提高了200倍。这些结果突出了合理连接体设计对于功能化的重要性。
