Control of Electronic Structure and Conductivity in Two-Dimensional Metal–Semiquinoid Frameworks of Titanium, Vanadium, and Chromium
Abstract
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.
- Authors:
-
- 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:
- 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.
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.
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.
@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}
}
Web of Science
Figures / Tables:

Works referencing / citing this record:
Coordination‐driven self‐assembly of Cp*Rh‐Based Rectangles, Cages and Their Host−Guest Binding Study
journal, April 2019
- Lin, Lin; Lin, Yue‐Jian; Jin, Guo‐Xin
- Applied Organometallic Chemistry, Vol. 33, Issue 7
Square Grid Metal–Chloranilate Networks as Robust Host Systems for Guest Sorption
journal, March 2019
- Kingsbury, Christopher J.; Abrahams, Brendan F.; Auckett, Josie E.
- Chemistry – A European Journal, Vol. 25, Issue 20
Two-dimensional magnetic materials of cobalt( ii ) triangular lattices constructed by a mixed benzimidazole–dicarboxylate strategy
journal, January 2019
- Kong, Jiao-Jiao; Jiang, Yu-Xuan; Zhang, Jia-Chen
- CrystEngComm, Vol. 21, Issue 15
Reversible redox switching of magnetic order and electrical conductivity in a 2D manganese benzoquinoid framework
journal, January 2019
- Liu, Lujia; DeGayner, Jordan A.; Sun, Lei
- Chemical Science, Vol. 10, Issue 17
Redox-active metal–organic frameworks for energy conversion and storage
journal, January 2019
- Calbo, Joaquín; Golomb, Matthias J.; Walsh, Aron
- Journal of Materials Chemistry A, Vol. 7, Issue 28
Efficient and tunable one-dimensional charge transport in layered lanthanide metal–organic frameworks
journal, November 2019
- Skorupskii, Grigorii; Trump, Benjamin A.; Kasel, Thomas W.
- Nature Chemistry, Vol. 12, Issue 2
A Series of Early Lanthanide Chloranilate Frameworks with a Square Grid Topology
journal, January 2019
- Hua, Carol; Tay, Hui Min; He, Qilin
- Australian Journal of Chemistry, Vol. 72, Issue 10
Coordination‐driven self‐assembly of Cp*Rh‐Based Rectangles, Cages and Their Host−Guest Binding Study
journal, April 2019
- Lin, Lin; Lin, Yue‐Jian; Jin, Guo‐Xin
- Applied Organometallic Chemistry, Vol. 33, Issue 7
Square Grid Metal–Chloranilate Networks as Robust Host Systems for Guest Sorption
journal, March 2019
- Kingsbury, Christopher J.; Abrahams, Brendan F.; Auckett, Josie E.
- Chemistry – A European Journal, Vol. 25, Issue 20
Efficient and tunable one-dimensional charge transport in layered lanthanide metal–organic frameworks
journal, November 2019
- Skorupskii, Grigorii; Trump, Benjamin A.; Kasel, Thomas W.
- Nature Chemistry, Vol. 12, Issue 2
Two-dimensional magnetic materials of cobalt( ii ) triangular lattices constructed by a mixed benzimidazole–dicarboxylate strategy
journal, January 2019
- Kong, Jiao-Jiao; Jiang, Yu-Xuan; Zhang, Jia-Chen
- CrystEngComm, Vol. 21, Issue 15
Reversible redox switching of magnetic order and electrical conductivity in a 2D manganese benzoquinoid framework
journal, January 2019
- Liu, Lujia; DeGayner, Jordan A.; Sun, Lei
- Chemical Science, Vol. 10, Issue 17
Redox-active metal–organic frameworks for energy conversion and storage
journal, January 2019
- Calbo, Joaquín; Golomb, Matthias J.; Walsh, Aron
- Journal of Materials Chemistry A, Vol. 7, Issue 28
A Series of Early Lanthanide Chloranilate Frameworks with a Square Grid Topology
journal, January 2019
- Hua, Carol; Tay, Hui Min; He, Qilin
- Australian Journal of Chemistry, Vol. 72, Issue 10
Synthetic investigation of competing magnetic interactions in 2D metal–chloranilate radical frameworks
journal, January 2020
- Collins, Kelsey A.; Saballos, Richard J.; Fataftah, Majed S.
- Chemical Science
A new fluorone-based bridging ligand for discrete and polymeric assemblies including Mo and W based [4+4] metallocycles
journal, January 2020
- Sutton, Ashley L.; Abrahams, Brendan F.; Hudson, Timothy A.
- New Journal of Chemistry, Vol. 44, Issue 27
Recent Development and Application of Conductive MOFs
journal, August 2018
- Li, Pengfei; Wang, Bo
- Israel Journal of Chemistry, Vol. 58, Issue 9-10
Conductive two-dimensional metal–organic frameworks as multifunctional materials
journal, January 2018
- Ko, Michael; Mendecki, Lukasz; Mirica, Katherine A.
- Chemical Communications, Vol. 54, Issue 57
Redox, transmetalation, and stacking properties of tetrathiafulvalene-2,3,6,7-tetrathiolate bridged tin, nickel, and palladium compounds
journal, January 2020
- Xie, Jiaze; Boyn, Jan-Niklas; Filatov, Alexander S.
- Chemical Science, Vol. 11, Issue 4
Zirconium metal–organic frameworks incorporating tetrathiafulvalene linkers: robust and redox-active matrices for in situ confinement of metal nanoparticles
journal, January 2020
- Su, Jian; Yuan, Shuai; Wang, Tao
- Chemical Science, Vol. 11, Issue 7
Coordination polymer-based conductive materials: ionic conductivity vs. electronic conductivity
journal, January 2019
- Wang, Hai-Ning; Meng, Xing; Dong, Long-Zhang
- Journal of Materials Chemistry A, Vol. 7, Issue 42
Theoretical discovery of Dirac half metal in experimentally synthesized two dimensional metal semiquinoid frameworks
journal, January 2019
- Tang, Cheng; Zhang, Chunmei; Jiang, Zhenyi
- Journal of Materials Chemistry C, Vol. 7, Issue 19