Lu Yang, Zhang Yingying, Yang Chi-Yuan, Revuelta Sergio, Qi Haoyuan, Huang Chuanhui, Jin Wenlong, Li Zichao, Vega-Mayoral Victor, Liu Yannan, Huang Xing, Pohl Darius, Položij Miroslav, Zhou Shengqiang, Cánovas Enrique, Heine Thomas, Fabiano Simone, Feng Xinliang, Dong Renhao
Center for Advancing Electronics Dresden & Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany.
Laboratory of Organic Electronics, Department of Science and Technology, Linköping University, Norrköping, Sweden.
Nat Commun. 2022 Nov 24;13(1):7240. doi: 10.1038/s41467-022-34820-6.
Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interests for (opto)-electronics and spintronics. They generally consist of van der Waals stacked layers and exhibit layer-depended electronic properties. While considerable efforts have been made to regulate the charge transport within a layer, precise control of electronic coupling between layers has not yet been achieved. Herein, we report a strategy to precisely tune interlayer charge transport in 2D c-MOFs via side-chain induced control of the layer spacing. We design hexaiminotriindole ligands allowing programmed functionalization with tailored alkyl chains (HATI_CX, X = 1,3,4; X refers to the carbon numbers of the alkyl chains) for the synthesis of semiconducting Ni(HATI_CX). The layer spacing of these MOFs can be precisely varied from 3.40 to 3.70 Å, leading to widened band gap, suppressed carrier mobilities, and significant improvement of the Seebeck coefficient. With this demonstration, we further achieve a record-high thermoelectric power factor of 68 ± 3 nW m K in Ni(HATI_C3), superior to the reported holes-dominated MOFs.
二维共轭金属有机框架（2D c-MOFs）在（光）电子学和自旋电子学领域引起了越来越多的关注。它们通常由范德华堆叠层组成，并表现出依赖于层的电子特性。尽管人们已经做出了相当大的努力来调节层内的电荷传输，但尚未实现对层间电子耦合的精确控制。在此，我们报告了一种通过侧链诱导控制层间距来精确调节2D c-MOFs中层间电荷传输的策略。我们设计了六亚氨基三吲哚配体，允许用定制的烷基链（HATI_CX，X = 1,3,4；X指烷基链的碳原子数）进行程序化功能化，用于合成半导体Ni(HATI_CX)。这些MOFs的层间距可以精确地从3.40埃变化到3.70埃，导致带隙变宽、载流子迁移率受到抑制，以及塞贝克系数显著提高。通过这一演示，我们进一步在Ni(HATI_C3)中实现了创纪录的68±3 nW m K的热电功率因子，优于报道的以空穴为主的MOFs。
