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Two-dimensional d-π conjugated metal-organic framework based on hexahydroxytrinaphthylene

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Abstract

The development of new two-dimensional (2D) d-π conjugated metal-organic frameworks (MOFs) holds great promise for the construction of a new generation of porous and semiconductive materials. This paper describes the synthesis, structural characterization, and electronic properties of a new d-π conjugated 2D MOF based on the use of a new ligand 2,3,8,9,14,15-hexahydroxytrinaphthylene. The reticular self-assembly of this large π-conjugated organic building block with Cu(II) ions in a mixed solvent system of 1,3-dimethyl-2-imidazolidinone (DMI) and H2O with the addition of ammonia water or ethylenediamine leads to a highly crystalline MOF Cu3(HHTN)2, which possesses pore aperture of 2.5 nm. Cu3(HHTN)2 MOF shows moderate electrical conductivity of 9.01 × 10−8 S·cm−1 at 385 K and temperature-dependent band gap ranging from 0.75 to 1.65 eV. After chemical oxidation by I2, the conductivity of Cu3(HHTN)2 can be increased by 360 times. This access to HHTN based MOF adds an important member to previously reported MOF systems with hexagonal lattice, paving the way towards systematic studies of structure-property relationships of semiconductive MOFs.

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Acknowledgements

The authors acknowledge support from startup funds provided by Dartmouth College, from the Walter and Constance Burke Research Initiation Award, Irving Institute for Energy and Society, Army Research Office Young Investigator Program Grant No. W911NF-17-1-0398, Sloan Research Fellowship (No. FG-2018-10561), 3M Non-Tenured Faculty Award, and US Army Cold Regions Research & Engineering Lab (No. W913E519C0008), National Science Foundation EPSCoR award (No. #1757371). The authors thank the University Instrumentation Center at the University of New Hampshire (Durham, NH, USA) for the access to XPS.

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  1. Department of Chemistry, Burke Laboratory, Dartmouth College, 41 College Street, Hanover, NH, 03755, USA

    Zheng Meng & Katherine A. Mirica

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Meng, Z., Mirica, K.A. Two-dimensional d-π conjugated metal-organic framework based on hexahydroxytrinaphthylene. Nano Res. 14, 369–375 (2021). https://doi.org/10.1007/s12274-020-2874-x

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