An Electrically Conductive Tetrathiafulvalene-Based Hydrogen-Bonded Organic Framework
An Electrically Conductive Tetrathiafulvalene-Based Hydrogen-Bonded Organic Framework
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DOI：
10.1021/acsmaterialslett.1c00628
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发表时间：
2021-12-07
影响因子：
11.4
通讯作者：
Farha, Omar K.
中科院分区：
文献类型：
--
作者：
Kirlikovali, Kent O.;Goswami, Subhadip;Farha, Omar K.
导电金属有机框架（MOFs）和共价有机框架（COFs）的发展最近取得了进展，由于与这些材料相关的固有可调谐性、孔隙率和结晶度，利用电子材料的各种应用引起了人们的兴趣。氢键键合有机框架（HOFs）包括一类新兴的互补多孔材料，其主要通过分子间氢键相互作用组装结晶网络;然而，关于功能HOFs的报道相对较少，因为这些可逆相互作用比在前一种框架中发现的配位或共价键弱得多，这在HOFs的分离和活化方面提出了额外的挑战。在这项工作中，我们介绍了一种方法来获得一个永久多孔霍夫衍生自四硫富瓦烯（TTF）的核心，这是第一个霍夫报道的日期，显示出导电性。在从溶液中沉淀时，霍夫-110以包含TTF二聚体的垂直柱的优选取向自组装，并且在该框架的纳米多孔通道内合成后掺入碘提供了高达6.0 × 10 - 7 Smiddotcm-1的压制颗粒电导率值，这与原始框架的压制颗粒相比几乎提高了30倍。广泛的结构表征研究表明，在这些材料中存在自由基混合价TTF/TTFmiddot+物质，这与以前关于类似的基于TTF的MOFs和COFs的报道一致。总的来说，这项工作提出了一个可行的战略，开发强大的，导电的框架建立从纯粹intermolecularinteractions，进一步扩大了工具箱可用于组装功能性多孔材料。
Recent advancements in the development of conductive metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) havesparked interest in a variety of applications that leverage electronic materials dueto the inherent tunability, porosity, and crystallinity associated with thesematerials. Hydrogen-bonded organic frameworks (HOFs) comprise an emergingclass of complementary porous materials that assemble crystalline networksmainly from intermolecular hydrogen-bonding interactions; however, relativelyfew reports on functional HOFs exist as these reversible interactions are muchweaker than the coordination or covalent bonds found in the former frameworks,which presents additional challenges in the isolation and activation of HOFs. Inthis work, we introduce an approach to access a permanently porous HOF derivedfrom a tetrathiafulvalene (TTF) core, which is thefirst HOF reported to date that exhibits electrical conductivity. Uponprecipitation from solution, HOF-110 self-assembles in a preferred orientation that contains vertical columns of TTF dimers,and the postsynthetic incorporation of iodine within the nanoporous channels of this framework affords pressed pelletconductivity values of up to 6.0x10-7Smiddotcm-1, which is an almost 30-fold improvement compared with pressed pellets of thepristine framework. Extensive structural characterization studies suggest the presence of radical mixed-valence TTF/TTFmiddot+species within these materials, which is consistent with previous reports on analogous TTF-based MOFs and COFs. Overall,this work presents a viable strategy to develop robust, electrically conductive frameworks built from purely intermolecularinteractions, further expanding the toolbox available for the assembly of functional porous materials.