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^–2 S cm^–1. Harnessing sulfur chemistry in Cu-thiaTRX involves a two-step postsynthetic modification: oxidation and S_NAr. 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.

中文翻译：

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基于噻虫烯的导电 MOF：利用硫化学增强质子传输


对导电 MOF (EC-MOF) 的有机构件进行功能化是调整电子结构和引入特定化学成分的有效方法。然而，由于 dp 缀合的要求，设计具有反应性官能团的 EC-MOF 连接体进行合成后修饰具有挑战性。这项工作通过合成 EC-MOF、Cu-thiatruxene (Cu-thiaTRX) 解决了此类设计限制。该导电框架结合了基于 truxene 的连接体和杂环硫，可实现高效共轭，电导率为 2.2 × 10 ^–2 S cm ^–1 。利用 Cu-thiaTRX 中的硫化学涉及两步合成后修饰：氧化和 S _N Ar。框架中引入的亚磺酸基团实现了可调节的质子电导率，从而使质子电导率提高了 200 倍。这些结果凸显了合理的连接子设计对于功能化的重要性。