Linker Aromaticity Reduces Band Dispersion in 2D Conductive Metal–Organic Frameworks,ACS Materials Letters

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Linker Aromaticity Reduces Band Dispersion in 2D Conductive Metal–Organic Frameworks
ACS Materials Letters ( IF 9.6 ) Pub Date : 2023-04-12 , DOI: 10.1021/acsmaterialslett.3c00122
Monique C. Demuth ₁ , Christopher H. Hendon ₁

Affiliation

All 2D electrically conductive metal–organic frameworks (MOFs) are constructed from hexasubstituted aromatics that oxidize during self-assembly. Since electrical conduction is thought to occur through the ligand π-system, but aromaticity itself results in stabilized π-electrons, the delocalization of ligand wavefunctions should be inversely related to the ligand π-stability. That is, aromatic π-electrons should prefer to localize on a single linker rather than delocalize to form a curved band in the MOF. Here, we use a combination of NICS-xy scans and bulk electronic band structure calculations to show that the extent of residual aromaticity in the oxidized linker is a good predictor for electronic localization in the resultant MOF. Thus, ligands that feature antiaromatic π-systems in the oxidation state found within the MOF should yield increased band curvature, a target parameter that affects charge mobility in high performing electrical conductors.

中文翻译：

链接剂芳香性降低了二维导电金属-有机骨架中的能带色散

所有二维导电金属有机骨架 (MOF) 均由在自组装过程中氧化的六取代芳烃构成。由于导电被认为是通过配体 π 系统发生的，但芳香性本身会导致稳定的 π 电子，因此配体波函数的离域化应该与配体 π 稳定性成反比。也就是说，芳香族 π 电子应该更喜欢定位在单个连接器上，而不是离域以在 MOF 中形成弯曲的带。在这里，我们结合使用 NICS-xy 扫描和整体电子能带结构计算来表明氧化连接体中残留芳香性的程度可以很好地预测所得 MOF 中的电子定位。因此，

更新日期：2023-04-12

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