Two-dimensional semiconducting covalent organic frameworks via condensation at arylmethyl carbon atoms
Two-dimensional semiconducting covalent organic frameworks via condensation at arylmethyl carbon atoms
复制标题
通过芳甲基碳原子缩合形成二维半导体共价有机骨架
DOI：
10.1038/s41467-019-10504-6
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发表时间：
2019-06-06
影响因子：
16.6
通讯作者：
Zhang, Fan
中科院分区：
文献类型：
--
作者：
Bi, Shuai;Yang, Can;Zhang, Fan
对于强大的光电转换，极其需要构建具有面内π-共辄结构和通过碳-碳键连接的鲁棒性的有机半导体材料，或者作为有机石墨烯类似物。然而，sp（2）碳键形成反应的不良可逆性使得它们不能用于通过自修复过程构建高结晶的明确定义的有机结构，例如共价有机框架（COF）。在这里，我们报告了一种可扩展的溶液处理方法，以基于3，5-二氰基-2，4，6-三甲基吡啶和线性/三角醛（即，4，4“-二甲酰基-对-三联苯、4，4”-二甲酰基-1，1“-联苯或1，3，5-三（4-甲酰基苯基）苯）单体。这种sp（2）碳连接的吡啶基框架，具有高表面积的结晶蜂窝状结构，能够在可见光照射下分别驱动两个水裂解的半反应，与石墨碳氮化物（g-C3 N4）衍生物相当。
Construction of organic semiconducting materials with in-plane it-conjugated structures and robustness through carbon-carbon bond linkages, alternatively as organic graphene analogs, is extremely desired for powerfully optoelectrical conversion. However, the poor reversibility for sp(2) carbon bond forming reactions makes them unavailable for building high crystalline well-defined organic structures through a self-healing process, such as covalent organic frameworks (COFs). Here we report a scalable solution-processing approach to synthesize a family of two-dimensional (2D) COFs with trans-disubstituted C = C linkages via condensation reaction at arylmethyl carbon atoms on the basis of 3,5-dicyano-2,4,6-trimethylpyridine and linear/trigonal aldehyde (i.e., 4,4 ''-diformyl-p-terphenyl, 4,4'-diformyl-1,1'-biphenyl, or 1,3,5-tris(4-formylphenyl)benzene) monomers. Such sp(2) carbon-jointedpyridinyl frameworks, featuring crystalline honeycomb-like structures with high surface areas, enable driving two half-reactions of water splitting separately under visible light irradiation, comparable to graphitic carbon nitride (g-C3N4) derivatives.