Control of Electronic Structure and Conductivity in Two-Dimensional Metal–Semiquinoid Frameworks of Titanium, Vanadium, and Chromium

doi:10.1021/jacs.7b13510

Title: Control of Electronic Structure and Conductivity in Two-Dimensional Metal–Semiquinoid Frameworks of Titanium, Vanadium, and Chromium

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Abstract

The isostructural, two-dimensional metal–organic frameworks (H ₂NMe ₂) ₂M2(Cl ₂dhbq) ₃ (M = Ti, V; Cl ₂dhbqn- = deprotonated 2,5-dichloro-3,6-dihydroxybenzoquinone) and (H ₂NMe ₂) _1.5Cr ₂(dhbq) ₃ (dhbq ^n- = deprotonated 2,5-dihydroxybenzoquinone) are synthesized and investigated by spectroscopic, magnetic, and electrochemical methods. The three frameworks exhibit substantial differences in their electronic structures, and the bulk electronic conductivities of these phases correlate with the extent of delocalization observed via UV–vis–NIR and IR spectroscopies. Notably, substantial metal–ligand covalency in the vanadium phase results in the quenching of ligand-based spins, the observation of simultaneous metal- and ligand-based redox processes, and a high electronic conductivity of 0.45 S/cm. In conclusion, a molecular orbital analysis of these materials and a previously reported iron congener suggests that the differences in conductivity can be explained by correlating the metal–ligand energy alignment with the energy of intervalence charge transfer transitions, which should determine the barrier to charge hopping in the mixed-valence frameworks.

Authors:

Ziebel, Michael E. ^[1]; Darago, Lucy E. ^[1];

^[2]

Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry and Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division

Publication Date:: 2018-02-05

Research Org.:: Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

OSTI Identifier:: 1460997

Grant/Contract Number:: SC0008688

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 140; Journal Issue: 8; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Ziebel, Michael E., Darago, Lucy E., and Long, Jeffrey R. Control of Electronic Structure and Conductivity in Two-Dimensional Metal–Semiquinoid Frameworks of Titanium, Vanadium, and Chromium.  United States: N. p., 2018. 
        Web.  doi:10.1021/jacs.7b13510.

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                    Ziebel, Michael E., Darago, Lucy E., & Long, Jeffrey R. Control of Electronic Structure and Conductivity in Two-Dimensional Metal–Semiquinoid Frameworks of Titanium, Vanadium, and Chromium.  United States.  doi:10.1021/jacs.7b13510.

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                    Ziebel, Michael E., Darago, Lucy E., and Long, Jeffrey R. Mon .  
        "Control of Electronic Structure and Conductivity in Two-Dimensional Metal–Semiquinoid Frameworks of Titanium, Vanadium, and Chromium".  United States.  doi:10.1021/jacs.7b13510.  https://www.osti.gov/servlets/purl/1460997.

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@article{osti_1460997,

  title        = {Control of Electronic Structure and Conductivity in Two-Dimensional Metal–Semiquinoid Frameworks of Titanium, Vanadium, and Chromium},

  author       = {Ziebel, Michael E. and Darago, Lucy E. and Long, Jeffrey R.},

  abstractNote = {The isostructural, two-dimensional metal–organic frameworks (H2NMe2)2M2(Cl2dhbq)3 (M = Ti, V; Cl2dhbqn- = deprotonated 2,5-dichloro-3,6-dihydroxybenzoquinone) and (H2NMe2)1.5Cr2(dhbq)3 (dhbqn- = deprotonated 2,5-dihydroxybenzoquinone) are synthesized and investigated by spectroscopic, magnetic, and electrochemical methods. The three frameworks exhibit substantial differences in their electronic structures, and the bulk electronic conductivities of these phases correlate with the extent of delocalization observed via UV–vis–NIR and IR spectroscopies. Notably, substantial metal–ligand covalency in the vanadium phase results in the quenching of ligand-based spins, the observation of simultaneous metal- and ligand-based redox processes, and a high electronic conductivity of 0.45 S/cm. In conclusion, a molecular orbital analysis of these materials and a previously reported iron congener suggests that the differences in conductivity can be explained by correlating the metal–ligand energy alignment with the energy of intervalence charge transfer transitions, which should determine the barrier to charge hopping in the mixed-valence frameworks.},

  doi          = {10.1021/jacs.7b13510},

  journal      = {Journal of the American Chemical Society},

  number       = 8,

  volume       = 140,

  place        = {United States},

  year         = {2018},

  month        = {2}

}

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