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Noncovalent ?-stacked robust topological organic framework.

ABSTRACT: Organic frameworks (OFs) offer a novel strategy for assembling organic semiconductors into robust networks that facilitate transport, especially the covalent organic frameworks (COFs). However, poor electrical conductivity through covalent bonds and insolubility of COFs limit their practical applications in organic electronics. It is known that the two-dimensional intralayer ????? transfer dominates transport in organic semiconductors. However, because of extremely labile inherent features of noncovalent ????? interaction, direct construction of robust frameworks via noncovalent ????? interaction is a difficult task. Toward this goal, we report a robust noncovalent ????? interaction-stacked organic framework, namely ?OF, consisting of a permanent three-dimensional porous structure that is held together by pure intralayer noncovalent ????? interactions. The elaborate porous structure, with a 1.69-nm supramaximal micropore, is composed of fully conjugated rigid aromatic tetragonal-disphenoid-shaped molecules with four identical platforms. ?OF shows excellent thermostability and high recyclability and exhibits self-healing properties by which the parent porosity is recovered upon solvent annealing at room temperature. Taking advantage of the long-range ????? interaction, we demonstrate remarkable transport properties of ?OF in an organic-field-effect transistor, and the mobility displays relative superiority over the traditional COFs. These promising results position ?OF in a direction toward porous and yet conductive materials for high-performance organic electronics.

SUBMITTER: Meng D

PROVIDER: S-EPMC7456091 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Noncovalent π-stacked robust topological organic framework.

Meng Dong D Yang Jonathan Lee JL Xiao Chengyi C Wang Rui R Xing Xiaofei X Kocak Olkan O Aydin Gulsevim G Yavuz Ilhan I Nuryyeva Selbi S Zhang Lei L Liu Guogang G Li Zhenxing Z Yuan Shuai S Wang Zhao-Kui ZK Wei Wei W Wang Zhaohui Z Houk K N KN Yang Yang Y

Proceedings of the National Academy of Sciences of the United States of America 20200811 34

Organic frameworks (OFs) offer a novel strategy for assembling organic semiconductors into robust networks that facilitate transport, especially the covalent organic frameworks (COFs). However, poor electrical conductivity through covalent bonds and insolubility of COFs limit their practical applications in organic electronics. It is known that the two-dimensional intralayer π∙∙∙π transfer dominates transport in organic semiconductors. However, because of extremely labile inherent features of no ...[more]

PMID: 32788358

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Project description:Achieving a molecular-level understanding of how the structures and compositions of metal-organic frameworks (MOFs) influence their charge carrier concentration and charge transport mechanism-the two key parameters of electrical conductivity-is essential for the successful development of electrically conducting MOFs, which have recently emerged as one of the most coveted functional materials due to their diverse potential applications in advanced electronics and energy technologies. Herein, we have constructed four new alkali metal (Na, K, Rb, and Cs) frameworks based on an electron-rich tetrathiafulvalene tetracarboxylate (TTFTC) ligand, which formed continuous π-stacks, albeit with different π-π-stacking and S⋯S distances (d π-π and d S⋯S). These MOFs also contained different amounts of aerobically oxidized TTFTC˙+ radical cations that were quantified by electron spin resonance (ESR) spectroscopy. Density functional theory calculations and diffuse reflectance spectroscopy demonstrated that depending on the π-π-interaction and TTFTC˙+ population, these MOFs enjoyed varying degrees of TTFTC/TTFTC˙+ intervalence charge transfer (IVCT) interactions, which commensurately affected their electronic and optical band gaps and electrical conductivity. Having the shortest d π-π (3.39 Å) and the largest initial TTFTC˙+ population (∼23%), the oxidized Na-MOF 1-ox displayed the narrowest band gap (1.33 eV) and the highest room temperature electrical conductivity (3.6 × 10-5 S cm-1), whereas owing to its longest d π-π (3.68 Å) and a negligible TTFTC˙+ population, neutral Cs-MOF 4 exhibited the widest band gap (2.15 eV) and the lowest electrical conductivity (1.8 × 10-7 S cm-1). The freshly prepared but not optimally oxidized K-MOF 2 and Rb-MOF 3 initially displayed intermediate band gaps and conductivity, however, upon prolonged aerobic oxidation, which raised the TTFTC˙+ population to saturation levels (∼25 and 10%, respectively), the resulting 2-ox and 3-ox displayed much narrower band gaps (∼1.35 eV) and higher electrical conductivity (6.6 × 10-5 and 4.7 × 10-5 S cm-1, respectively). The computational studies indicated that charge movement in these MOFs occurred predominantly through the π-stacked ligands, while the experimental results displayed the combined effects of π-π-interactions, TTFTC˙+ population, and TTFTC/TTFTC˙+ IVCT interaction on their electronic and optical properties, demonstrating that IVCT interactions between the mixed-valent ligands could be exploited as an effective design strategy to develop electrically conducting MOFs.

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Noncovalent ?-stacked robust topological organic framework.

Publications

Noncovalent π-stacked robust topological organic framework.

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