Electrically Conductive π‐Intercalated Graphitic Metal‐Organic Framework Containing Alternate π‐Donor/Acceptor Stacks
Electrically Conductive π‐Intercalated Graphitic Metal‐Organic Framework Containing Alternate π‐Donor/Acceptor Stacks
复制标题
导电性插层石墨金属——含有交替供体/受体堆栈的有机框架
DOI：
10.1002/anie.202303819
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Saha, Sourav
中科院分区：
文献类型：
--
作者：
Yadav, Ashok;Zhang, Shiyu;Benavides, Paola A.;Zhou, Wei;Saha, Sourav
二维石墨金属有机框架（GMOF）通常表现出令人印象深刻的导电性，这主要是由于其有效的平面内电荷通过键传输，然而，在堆叠层上的低效率的平面外传导造成了两种正交传导途径之间的巨大差异，并抑制了它们的整体导电性。为了解决这一问题并在二维GMOF中设计更高的体积导电性，我们通过一种优雅的自下而上的方法构建了第一个π‐插层GMOF (iGMOF1)，其特征是内置的交替π‐供体/受体（π‐D/A）堆叠的CuII‐配位富电子六氨基三苯（HATP）配体和非配位插层π‐酸性六氨基三苯（HCTP）分子。这促进了面外电荷传输，而六边形Cu3(HATP)2支架则维持了面内传导。结果表明，iGMOF1获得了比Cu3(HATP)2高一个数量级的体积电导率和小得多的活化能（σ=25 vs. 2 S m−1,Ea=36 vs. 65 meV），表明同时在平面内（通过键）和平面外（通过πD/ a堆叠）的电荷传输可以在新型iGMOFs中产生更高的电导率。
Two‐dimensional graphitic metal–organic frameworks (GMOF) often display impressive electrical conductivity chiefly due to efficient through‐bond in‐plane charge transport, however, less efficient out‐of‐plane conduction across the stacked layers creates large disparity between two orthogonal conduction pathways and dampens their bulk conductivity. To address this issue and engineer higher bulk conductivity in 2D GMOFs, we have constructed via an elegant bottom‐up method the first π‐intercalated GMOF (iGMOF1) featuring built‐in alternate π‐donor/acceptor (π‐D/A) stacks of CuII‐coordinated electron‐rich hexaaminotriphenylene (HATP) ligands and non‐coordinatively intercalated π‐acidic hexacyano‐triphenylene (HCTP) molecules, which facilitated out‐of‐plane charge transport while the hexagonal Cu3(HATP)2scaffold maintained in‐plane conduction. As a result, iGMOF1 attained an order of magnitude higher bulk electrical conductivity and much smaller activation energy than Cu3(HATP)2(σ=25 vs. 2 S m−1,Ea=36 vs. 65 meV), demostrating that simultaneous in‐plane (through‐bond) and out‐of‐plane (through πD/A stacks) charge transport can generate higher electrical conductivity in novel iGMOFs.