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Title: Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework

Abstract

Here, a three-dimensional network solid composed of FeIII centers and paramagnetic semiquinoid linkers, (NBu4)2FeIII2(dhbq)3 (dhbq2–/3– = 2,5-dioxidobenzoquinone/1,2-dioxido-4,5-semiquinone), is shown to exhibit a conductivity of 0.16 ± 0.01 S/cm at 298 K, one of the highest values yet observed for a metal–organic framework (MOF). The origin of this electronic conductivity is determined to be ligand mixed-valency, which is characterized using a suite of spectroscopic techniques, slow-scan cyclic voltammetry, and variable-temperature conductivity and magnetic susceptibility measurements. Importantly, UV–vis–NIR diffuse reflectance measurements reveal the first observation of Robin–Day Class II/III mixed valency in a MOF. Pursuit of stoichiometric control over the ligand redox states resulted in synthesis of the reduced framework material Na0.9(NBu4)1.8FeIII2(dhbq)3. Differences in electronic conductivity and magnetic ordering temperature between the two compounds are investigated and correlated to the relative ratio of the two different ligand redox states. Overall, the transition metal–semiquinoid system is established as a particularly promising scaffold for achieving tunable long-range electronic communication in MOFs.

Authors:
 [1];  [1];  [1];  [1];  [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
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)
Contributing Org.:
Beamline 17-BM; Beamline 11.3.1
OSTI Identifier:
1488852
Grant/Contract Number:  
FG02-12ER16362; SC0008688
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 50; 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

Darago, Lucy E., Aubrey, Michael L., Yu, Chung Jui, Gonzalez, Miguel I., and Long, Jeffrey R.. Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework. United States: N. p., 2015. Web. https://doi.org/10.1021/jacs.5b10385.
Darago, Lucy E., Aubrey, Michael L., Yu, Chung Jui, Gonzalez, Miguel I., & Long, Jeffrey R.. Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework. United States. https://doi.org/10.1021/jacs.5b10385
Darago, Lucy E., Aubrey, Michael L., Yu, Chung Jui, Gonzalez, Miguel I., and Long, Jeffrey R.. Tue . "Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework". United States. https://doi.org/10.1021/jacs.5b10385. https://www.osti.gov/servlets/purl/1488852.
@article{osti_1488852,
title = {Electronic Conductivity, Ferrimagnetic Ordering, and Reductive Insertion Mediated by Organic Mixed-Valence in a Ferric Semiquinoid Metal–Organic Framework},
author = {Darago, Lucy E. and Aubrey, Michael L. and Yu, Chung Jui and Gonzalez, Miguel I. and Long, Jeffrey R.},
abstractNote = {Here, a three-dimensional network solid composed of FeIII centers and paramagnetic semiquinoid linkers, (NBu4)2FeIII2(dhbq)3 (dhbq2–/3– = 2,5-dioxidobenzoquinone/1,2-dioxido-4,5-semiquinone), is shown to exhibit a conductivity of 0.16 ± 0.01 S/cm at 298 K, one of the highest values yet observed for a metal–organic framework (MOF). The origin of this electronic conductivity is determined to be ligand mixed-valency, which is characterized using a suite of spectroscopic techniques, slow-scan cyclic voltammetry, and variable-temperature conductivity and magnetic susceptibility measurements. Importantly, UV–vis–NIR diffuse reflectance measurements reveal the first observation of Robin–Day Class II/III mixed valency in a MOF. Pursuit of stoichiometric control over the ligand redox states resulted in synthesis of the reduced framework material Na0.9(NBu4)1.8FeIII2(dhbq)3. Differences in electronic conductivity and magnetic ordering temperature between the two compounds are investigated and correlated to the relative ratio of the two different ligand redox states. Overall, the transition metal–semiquinoid system is established as a particularly promising scaffold for achieving tunable long-range electronic communication in MOFs.},
doi = {10.1021/jacs.5b10385},
journal = {Journal of the American Chemical Society},
number = 50,
volume = 137,
place = {United States},
year = {2015},
month = {11}
}

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Figures / Tables:

Figure 1. Figure 1.: Redox states of linkers deriving from 2,5- dihydroxybenzoquinone that have previously been observed in metal-organic molecules or coordination solids. Notably, dhbq3– is a paramagnetic radical bridging ligand.

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Works referenced in this record:

Isoreticular Expansion of Metal–Organic Frameworks with Triangular and Square Building Units and the Lowest Calculated Density for Porous Crystals
journal, September 2011

  • Furukawa, Hiroyasu; Go, Yong Bok; Ko, Nakeun
  • Inorganic Chemistry, Vol. 50, Issue 18, p. 9147-9152
  • DOI: 10.1021/ic201376t

Metal–Organic Framework Materials with Ultrahigh Surface Areas: Is the Sky the Limit?
journal, August 2012

  • Farha, Omar K.; Eryazici, Ibrahim; Jeong, Nak Cheon
  • Journal of the American Chemical Society, Vol. 134, Issue 36, p. 15016-15021
  • DOI: 10.1021/ja3055639

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
journal, January 2002

  • Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel
  • Science, Vol. 295, Issue 5554, p. 469-472
  • DOI: 10.1126/science.1067208

Metal–Organic Framework Materials as Chemical Sensors
journal, September 2011

  • Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K.
  • Chemical Reviews, Vol. 112, Issue 2, p. 1105-1125
  • DOI: 10.1021/cr200324t

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Metal–Organic Frameworks (MOFs)
journal, January 2014

  • Zhou, Hong-Cai “Joe”; Kitagawa, Susumu
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS90059F

Engineering Metal Organic Frameworks for Heterogeneous Catalysis
journal, August 2010

  • Corma, A.; García, H.; Llabrés i Xamena, F. X.
  • Chemical Reviews, Vol. 110, Issue 8, p. 4606-4655
  • DOI: 10.1021/cr9003924

Towards Conducting Metal-Organic Frameworks
journal, January 2011

  • D'Alessandro, Deanna M.; Kanga, Jehan R. R.; Caddy, James S.
  • Australian Journal of Chemistry, Vol. 64, Issue 6
  • DOI: 10.1071/CH11039

Metal organic frameworks for electrochemical applications
journal, January 2012

  • Morozan, Adina; Jaouen, Frédéric
  • Energy & Environmental Science, Vol. 5, Issue 11
  • DOI: 10.1039/c2ee22989g

Thin Film Thermoelectric Metal-Organic Framework with High Seebeck Coefficient and Low Thermal Conductivity
journal, April 2015

  • Erickson, Kristopher J.; Léonard, François; Stavila, Vitalie
  • Advanced Materials, Vol. 27, Issue 22
  • DOI: 10.1002/adma.201501078

Magnetic metal–organic frameworks
journal, January 2009

  • Kurmoo, Mohamedally
  • Chemical Society Reviews, Vol. 38, Issue 5, 1353-1379
  • DOI: 10.1039/b804757j

Microporous magnets
journal, January 2011

  • Dechambenoit, Pierre; Long, Jeffrey R.
  • Chemical Society Reviews, Vol. 40, Issue 6
  • DOI: 10.1039/c0cs00167h

Dynamic magnetic MOFs
journal, January 2013

  • Coronado, Eugenio; Mínguez Espallargas, Guillermo
  • Chem. Soc. Rev., Vol. 42, Issue 4
  • DOI: 10.1039/C2CS35278H

Electrical conductive coordination polymers
journal, January 2012

  • Givaja, Gonzalo; Amo-Ochoa, Pilar; Gómez-García, Carlos J.
  • Chem. Soc. Rev., Vol. 41, Issue 1
  • DOI: 10.1039/C1CS15092H

Electroconductive Porous Coordination Polymer Cu[Cu(pdt) 2 ] Composed of Donor and Acceptor Building Units
journal, October 2009

  • Takaishi, Shinya; Hosoda, Miyuki; Kajiwara, Takashi
  • Inorganic Chemistry, Vol. 48, Issue 19
  • DOI: 10.1021/ic802117q

Conductivity, Doping, and Redox Chemistry of a Microporous Dithiolene-Based Metal−Organic Framework
journal, July 2010

  • Kobayashi, Yoji; Jacobs, Benjamin; Allendorf, Mark D.
  • Chemistry of Materials, Vol. 22, Issue 14
  • DOI: 10.1021/cm101238m

Porous, Conductive Metal-Triazolates and Their Structural Elucidation by the Charge-Flipping Method
journal, June 2012

  • Gándara, Felipe; Uribe-Romo, Fernando J.; Britt, David K.
  • Chemistry - A European Journal, Vol. 18, Issue 34, p. 10595-10601
  • DOI: 10.1002/chem.201103433

High Charge Mobility in a Tetrathiafulvalene-Based Microporous Metal–Organic Framework
journal, July 2012

  • Narayan, Tarun C.; Miyakai, Tomoyo; Seki, Shu
  • Journal of the American Chemical Society, Vol. 134, Issue 31
  • DOI: 10.1021/ja3059827

Mn 2 (2,5-disulfhydrylbenzene-1,4-dicarboxylate): A Microporous Metal–Organic Framework with Infinite (−Mn–S−) Chains and High Intrinsic Charge Mobility
journal, May 2013

  • Sun, Lei; Miyakai, Tomoyo; Seki, Shu
  • Journal of the American Chemical Society, Vol. 135, Issue 22
  • DOI: 10.1021/ja4037516

Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices
journal, December 2013

  • Talin, A. Alec; Centrone, Andrea; Ford, Alexandra C.
  • Science, Vol. 343, Issue 6166, p. 66-69
  • DOI: 10.1126/science.1246738

Million-Fold Electrical Conductivity Enhancement in Fe 2 (DEBDC) versus Mn 2 (DEBDC) (E = S, O)
journal, May 2015

  • Sun, Lei; Hendon, Christopher H.; Minier, Mikael A.
  • Journal of the American Chemical Society, Vol. 137, Issue 19
  • DOI: 10.1021/jacs.5b02897

Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks
journal, January 2015

  • Park, Sarah S.; Hontz, Eric R.; Sun, Lei
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja512437u

New Porous Crystals of Extended Metal-Catecholates
journal, August 2012

  • Hmadeh, Mohamad; Lu, Zheng; Liu, Zheng
  • Chemistry of Materials, Vol. 24, Issue 18, p. 3511-3513
  • DOI: 10.1021/cm301194a

π-Conjugated Nickel Bis(dithiolene) Complex Nanosheet
journal, February 2013

  • Kambe, Tetsuya; Sakamoto, Ryota; Hoshiko, Ken
  • Journal of the American Chemical Society, Vol. 135, Issue 7
  • DOI: 10.1021/ja312380b

Redox Control and High Conductivity of Nickel Bis(dithiolene) Complex π-Nanosheet: A Potential Organic Two-Dimensional Topological Insulator
journal, October 2014

  • Kambe, Tetsuya; Sakamoto, Ryota; Kusamoto, Tetsuro
  • Journal of the American Chemical Society, Vol. 136, Issue 41
  • DOI: 10.1021/ja507619d

High Electrical Conductivity in Ni 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 , a Semiconducting Metal–Organic Graphene Analogue
journal, April 2014

  • Sheberla, Dennis; Sun, Lei; Blood-Forsythe, Martin A.
  • Journal of the American Chemical Society, Vol. 136, Issue 25
  • DOI: 10.1021/ja502765n

Cu 3 (hexaiminotriphenylene) 2 : An Electrically Conductive 2D Metal-Organic Framework for Chemiresistive Sensing
journal, February 2015

  • Campbell, Michael G.; Sheberla, Dennis; Liu, Sophie F.
  • Angewandte Chemie International Edition, Vol. 54, Issue 14
  • DOI: 10.1002/anie.201411854

A two-dimensional π–d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour
journal, June 2015

  • Huang, Xing; Sheng, Peng; Tu, Zeyi
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8408

Conductive metal–organic frameworks and networks: fact or fantasy?
journal, January 2012

  • Hendon, Christopher H.; Tiana, Davide; Walsh, Aron
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 38, p. 13120-13132
  • DOI: 10.1039/c2cp41099k

Coordination compounds of 1,4-dihydroxybenzoquinone and its homologues. Structures and properties
journal, January 2002


Spin Exchange Effects on the Physicochemical Properties of Tetraoxolene-Bridged Bimetallic Complexes
journal, April 2007

  • Guo, Dong; McCusker, James K.
  • Inorganic Chemistry, Vol. 46, Issue 8
  • DOI: 10.1021/ic070005y

Tetraoxolene radical stabilization by the interaction with transition-metal ions
journal, June 1991

  • Dei, Andrea.; Gatteschi, Dante.; Pardi, Luca.
  • Inorganic Chemistry, Vol. 30, Issue 12
  • DOI: 10.1021/ic00012a006

Characterization of the Chloranilate(•3−) π Radical as a Strong Spin-Coupling Bridging Ligand
journal, August 2006

  • Min, Kil Sik; Rheingold, Arnold L.; DiPasquale, Antonio
  • Inorganic Chemistry, Vol. 45, Issue 16
  • DOI: 10.1021/ic061076k

Observation of Redox-Induced Electron Transfer and Spin Crossover for Dinuclear Cobalt and Iron Complexes with the 2,5-Di- tert -butyl-3,6-dihydroxy-1,4-benzoquinonate Bridging Ligand
journal, May 2009

  • Min, Kil Sik; DiPasquale, Antonio G.; Rheingold, Arnold L.
  • Journal of the American Chemical Society, Vol. 131, Issue 17
  • DOI: 10.1021/ja900909u

Straightforward Synthesis of Substituted p -Quinones: Isolation of a Key Intermediate and Use as a Bridging Ligand in a Diruthenium Complex
journal, March 2010

  • Das, Hari Sankar; Weisser, Fritz; Schweinfurth, David
  • Chemistry - A European Journal, Vol. 16, Issue 10
  • DOI: 10.1002/chem.200903409

Coordination Polymers of 2,5-Dihydroxybenzoquinone and Chloranilic Acid with the (10,3)- a Topology
journal, July 2011

  • Abrahams, Brendan F.; Hudson, Timothy A.; McCormick, Laura J.
  • Crystal Growth & Design, Vol. 11, Issue 7
  • DOI: 10.1021/cg2005908

2D and 3D Anilato-Based Heterometallic M(I)M(III) Lattices: The Missing Link
journal, May 2015

  • Benmansour, Samia; Vallés-García, Cristina; Gómez-Claramunt, Patricia
  • Inorganic Chemistry, Vol. 54, Issue 11
  • DOI: 10.1021/acs.inorgchem.5b00451

A Novel Hybrid Supramolecular Network Assembled from Perfect ??? Stacking of an Anionic Inorganic Layer and a Cationic Hydronium-Ion-Mediated Organic Layer
journal, November 2004

  • Luo, Tzuoo-Tsair; Liu, Yen-Hsiang; Tsai, Hui-Lien
  • European Journal of Inorganic Chemistry, Vol. 2004, Issue 21
  • DOI: 10.1002/ejic.200400199

A Family of Layered Chiral Porous Magnets Exhibiting Tunable Ordering Temperatures
journal, August 2013

  • Atzori, Matteo; Benmansour, Samia; Mínguez Espallargas, Guillermo
  • Inorganic Chemistry, Vol. 52, Issue 17
  • DOI: 10.1021/ic4013284

Novel Intercalation Host System Based on Transition Metal (Fe 2+ , Co 2+ , Mn 2+ )−Chloranilate Coordination Polymers. Single Crystal Structures and Properties
journal, December 1998

  • Kawata, Satoshi; Kitagawa, Susumu; Kumagai, Hitoshi
  • Chemistry of Materials, Vol. 10, Issue 12
  • DOI: 10.1021/cm980326v

A Concept for the Synthesis of 3-Dimensional Homo- and Bimetallic Oxalate-Bridged Networks [M2(ox)3]n. Structural, Moessbauer, and Magnetic Studies in the Field of Molecular-Based Magnets
journal, October 1994

  • Decurtins, Silvio; Schmalle, Helmut W.; Schneuwly, Philippe
  • Journal of the American Chemical Society, Vol. 116, Issue 21
  • DOI: 10.1021/ja00100a016

Oxalate-Based 3D Chiral Magnets: The Series [ZII(bpy)3][ClO4][MIIFeIII(ox)3] (ZII = Fe, Ru; MII = Mn, Fe; bpy = 2,2'-Bipyridine; ox = Oxalate Dianion)
journal, June 2005

  • Coronado, Eugenio; Galán-Mascarós, José R.; Gómez-García, Carlos J.
  • European Journal of Inorganic Chemistry, Vol. 2005, Issue 11
  • DOI: 10.1002/ejic.200400977

Preparation of a semiquinonate-bridged diiron(ii) complex and elucidation of its geometric and electronic structures
journal, January 2013

  • Baum, Amanda E.; Lindeman, Sergey V.; Fiedler, Adam T.
  • Chemical Communications, Vol. 49, Issue 58
  • DOI: 10.1039/c3cc42980f

Structural and magnetic properties of tris(o-semiquinone) complexes of iron(III) and chromium(III)
journal, December 1978

  • Buchanan, Robert M.; Kessel, Stephen L.; Downs, Hartly H.
  • Journal of the American Chemical Society, Vol. 100, Issue 25
  • DOI: 10.1021/ja00493a018

Mixed-Valence Li/Fe-Based Metal–Organic Frameworks with Both Reversible Redox and Sorption Properties
journal, April 2007

  • Férey, Gérard; Millange, Franck; Morcrette, Mathieu
  • Angewandte Chemie International Edition, Vol. 46, Issue 18
  • DOI: 10.1002/anie.200605163

Synthesis, Structure, Characterization, and Redox Properties of the Porous MIL-68(Fe) Solid
journal, July 2010

  • Fateeva, Alexandra; Horcajada, Patricia; Devic, Thomas
  • European Journal of Inorganic Chemistry, Vol. 2010, Issue 24
  • DOI: 10.1002/ejic.201000486

Monitoring the Solid-State Electrochemistry of Cu(2,7-AQDC) (AQDC = Anthraquinone Dicarboxylate) in a Lithium Battery: Coexistence of Metal and Ligand Redox Activities in a Metal–Organic Framework
journal, November 2014

  • Zhang, Zhongyue; Yoshikawa, Hirofumi; Awaga, Kunio
  • Journal of the American Chemical Society, Vol. 136, Issue 46
  • DOI: 10.1021/ja508197w

MIL-101(Fe) as a lithium-ion battery electrode material: a relaxation and intercalation mechanism during lithium insertion
journal, January 2015

  • Shin, JaeWook; Kim, Min; Cirera, Jordi
  • Journal of Materials Chemistry A, Vol. 3, Issue 8
  • DOI: 10.1039/C4TA06694D

The Localized-to-Delocalized Transition in Mixed-Valence Chemistry
journal, September 2001

  • Demadis, Konstantinos D.; Hartshorn, Chris M.; Meyer, Thomas J.
  • Chemical Reviews, Vol. 101, Issue 9
  • DOI: 10.1021/cr990413m

Intervalence Charge Transfer (IVCT) in Trinuclear and Tetranuclear Complexes of Iron, Ruthenium, and Osmium
journal, June 2006

  • D'Alessandro, Deanna M.; Keene, F. Richard
  • Chemical Reviews, Vol. 106, Issue 6
  • DOI: 10.1021/cr050010o

Organic Mixed Valence
journal, August 2011

  • Hankache, Jihane; Wenger, Oliver S.
  • Chemical Reviews, Vol. 111, Issue 8
  • DOI: 10.1021/cr100441k

Reduction of a Metal-Organic Framework by an Organometallic Complex: Magnetic Properties and Structure of the Inclusion Compound [(η5-C5H5)2Co]0.5@MIL-47(V)
journal, July 2010

  • Meilikhov, Mikhail; Yusenko, Kirill; Torrisi, Antonio
  • Angewandte Chemie International Edition, Vol. 49, Issue 35
  • DOI: 10.1002/anie.200907126

Voltammetric reduction and re-oxidation of solid coordination polymers of dihydroxybenzoquinone
journal, January 2012

  • Abrahams, Brendan F.; Bond, Alan M.; Le, Thanh Hai
  • Chemical Communications, Vol. 48, Issue 93
  • DOI: 10.1039/c2cc34687g

Metal–Organic Framework Thin Films Composed of Free-Standing Acicular Nanorods Exhibiting Reversible Electrochromism
journal, December 2013

  • Kung, Chung-Wei; Wang, Timothy Chiaan; Mondloch, Joseph E.
  • Chemistry of Materials, Vol. 25, Issue 24
  • DOI: 10.1021/cm403726v

Facile Deposition of Multicolored Electrochromic Metal-Organic Framework Thin Films
journal, October 2013

  • Wade, Casey R.; Li, Minyuan; Dincă, Mircea
  • Angewandte Chemie International Edition, Vol. 52, Issue 50
  • DOI: 10.1002/anie.201306162

Ligand Redox Non-innocence in the Stoichiometric Oxidation of Mn 2 (2,5-dioxidoterephthalate) (Mn-MOF-74)
journal, February 2014

  • Cozzolino, Anthony F.; Brozek, Carl K.; Palmer, Ryan D.
  • Journal of the American Chemical Society, Vol. 136, Issue 9
  • DOI: 10.1021/ja411808r

Controlling charge separation in a novel donor–acceptor metal–organic framework via redox modulation
journal, January 2014

  • Leong, C. F.; Chan, B.; Faust, T. B.
  • Chem. Sci., Vol. 5, Issue 12
  • DOI: 10.1039/C4SC01551G

Magnetically ordered molecule-based materials
journal, January 2011


A Room-Temperature Molecular/Organic-Based Magnet
journal, June 1991


Glassy Magnets Composed of Metals Coordinated to 7,7,8,8-tetracyanoquinodimethane:  M(TCNQ) 2 (M = Mn, Fe, Co, Ni)
journal, May 2003

  • Clérac, Rodolphe; O'Kane, Shannon; Cowen, Jerry
  • Chemistry of Materials, Vol. 15, Issue 9
  • DOI: 10.1021/cm021053d

Ferrimagnetic Mixed-Valency and Mixed-Metal Tris(oxalato)iron(III) Compounds:  Synthesis, Structure, and Magnetism
journal, January 1996

  • Mathonière, Corine; Nuttall, Christopher J.; Carling, Simon G.
  • Inorganic Chemistry, Vol. 35, Issue 5
  • DOI: 10.1021/ic950703v

Molecules to build solids: high TC molecule-based magnets by design and recent revival of cyano complexes chemistry
journal, September 1999


The disodium salt of 2,5-dihydroxy-1,4-benzoquinone as anode material for rechargeable sodium ion batteries
journal, January 2015

  • Zhu, Zhiqiang; Li, Hao; Liang, Jing
  • Chemical Communications, Vol. 51, Issue 8
  • DOI: 10.1039/C4CC08220F

Calculating Geometric Surface Areas as a Characterization Tool for Metal−Organic Frameworks
journal, October 2007

  • Düren, Tina; Millange, Franck; Férey, Gérard
  • The Journal of Physical Chemistry C, Vol. 111, Issue 42
  • DOI: 10.1021/jp074723h

Magnetic Molecular Conductors
journal, November 2004

  • Coronado, Eugenio; Day, Peter
  • Chemical Reviews, Vol. 104, Issue 11
  • DOI: 10.1021/cr030641n

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    New functionalized acenaphthene-1,2-diimines and derived zinc and copper complexes
    journal, January 2020

    • Sokolov, V. G.; Moskalev, M. V.; Koptseva, T. S.
    • Russian Chemical Bulletin, Vol. 69, Issue 1
    • DOI: 10.1007/s11172-020-2733-7

    Semiconductor Metal-Organic Frameworks: Future Low-Bandgap Materials
    journal, November 2016

    • Usman, Muhammad; Mendiratta, Shruti; Lu, Kuang-Lieh
    • Advanced Materials, Vol. 29, Issue 6
    • DOI: 10.1002/adma.201605071

    A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity
    journal, March 2020

    • Jiang, Qiang; Xiong, Peixun; Liu, Jingjuan
    • Angewandte Chemie International Edition, Vol. 59, Issue 13
    • DOI: 10.1002/anie.201914395

    Solid–Gas Phase Synthesis of Coordination Networks by Using Redox‐Active Ligands and Elucidation of Their Oxidation Reaction
    journal, August 2019

    • Den, Taizen; Usov, Pavel M.; Kim, Jaejun
    • Chemistry – A European Journal, Vol. 25, Issue 49
    • DOI: 10.1002/chem.201902105

    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
    • DOI: 10.1039/c9ta08253k

    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
    • DOI: 10.1039/c9ta04680a

    Probing charge transfer characteristics in a donor–acceptor metal–organic framework by Raman spectroelectrochemistry and pressure-dependence studies
    journal, January 2018

    • Usov, Pavel M.; Leong, Chanel F.; Chan, Bun
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 40
    • DOI: 10.1039/c8cp04157a

    Syntheses, structures and magnetic properties of nine coordination polymers based on terphenyl-tetracarboxylic acid ligands
    journal, January 2017

    • Zhou, Xinhui; Chen, Qianqian; Liu, Baolin
    • Dalton Transactions, Vol. 46, Issue 2
    • DOI: 10.1039/c6dt04270h

    On‐surface Synthesis of a Semiconducting 2D Metal–Organic Framework Cu 3 (C 6 O 6 ) Exhibiting Dispersive Electronic Bands
    journal, January 2020


    A 1,2,3-dithiazolyl-o-naphthoquinone: a neutral radical with isolable cation and anion oxidation states
    journal, January 2016

    • Smithson, Chad S.; MacDonald, Daniel J.; Matt Letvenuk, T.
    • Dalton Transactions, Vol. 45, Issue 23
    • DOI: 10.1039/c6dt01249c

    Benzoquinone-bridged Co 2 complexes with different magnetic anisotropy induced by solvent molecules
    journal, January 2017

    • Cao, Wenhai; Zhu, Xiaoquan; Liu, Pengfei
    • Dalton Transactions, Vol. 46, Issue 11
    • DOI: 10.1039/c6dt04420d

    New Bromine-Containing Bis(arylimino)acenaphthenes and Related Metal Complexes
    journal, April 2020

    • Makarov, V. M.; Koptseva, T. S.; Sokolov, V. G.
    • Russian Journal of Coordination Chemistry, Vol. 46, Issue 4
    • DOI: 10.1134/s1070328420030045

    Strategies to Improve Electrical and Ionic Conductivities of Metal–Organic Frameworks
    journal, December 2019


    Electron delocalization and charge mobility as a function of reduction in a metal–organic framework
    journal, June 2018


    Cuboctahedron-based indium–organic frameworks for gas sorption and selective cation exchange
    journal, January 2016

    • Yu, Panpan; Li, Qipeng; Hu, Yue
    • Chemical Communications, Vol. 52, Issue 51
    • DOI: 10.1039/c6cc03497g

    Elucidating metal and ligand redox activities of a copper-benzoquinoid coordination polymer as the cathode for lithium-ion batteries
    journal, January 2019

    • Chang, Cheng-Han; Li, An-Che; Popovs, Ilja
    • Journal of Materials Chemistry A, Vol. 7, Issue 41
    • DOI: 10.1039/c9ta05244e

    Switchable electrical conductivity in a three-dimensional metal–organic framework via reversible ligand n-doping
    journal, January 2020

    • Wentz, Hanna C.; Skorupskii, Grigorii; Bonfim, Ana B.
    • Chemical Science, Vol. 11, Issue 5
    • DOI: 10.1039/c9sc06150a

    Integration of a (–Cu–S–)n plane in a metal–organic framework affords high electrical conductivity
    journal, April 2019


    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
    • DOI: 10.1039/d0nj02413a

    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
    • DOI: 10.1039/c8cc02871k

    A chlorine-free protocol for processing germanium
    journal, May 2017

    • Glavinović, Martin; Krause, Michael; Yang, Linju
    • Science Advances, Vol. 3, Issue 5
    • DOI: 10.1126/sciadv.1700149

    A microporous europium–organic framework anchored with open –COOH groups for selective cation sensing
    journal, January 2016

    • Qian, Jinjie; Yu, Panpan; Huang, Shaoming
    • CrystEngComm, Vol. 18, Issue 41
    • DOI: 10.1039/c6ce01801g

    Metal-Organic Frameworks-Based Electrocatalysis: Insight and Future Perspectives
    journal, September 2018


    Layer-by-Layer Assembled Conductive Metal-Organic Framework Nanofilms for Room-Temperature Chemiresistive Sensing
    journal, November 2017

    • Yao, Ming-Shui; Lv, Xiao-Jing; Fu, Zhi-Hua
    • Angewandte Chemie International Edition, Vol. 56, Issue 52
    • DOI: 10.1002/anie.201709558

    Ligand mixed-valence and electrical conductivity in coordination complexes containing a redox-active phenalenol-substituted ligand
    journal, January 2019

    • Dale, Sarah; Bonanno, Nico M.; Pelaccia, Mark
    • Dalton Transactions, Vol. 48, Issue 23
    • DOI: 10.1039/c9dt01788g

    A Dual‐Ligand Porous Coordination Polymer Chemiresistor with Modulated Conductivity and Porosity
    journal, January 2020

    • Yao, Ming‐Shui; Zheng, Jia‐Jia; Wu, Ai‐Qian
    • Angewandte Chemie International Edition, Vol. 59, Issue 1
    • DOI: 10.1002/anie.201909096

    Mechano-regulated metal–organic framework nanofilm for ultrasensitive and anti-jamming strain sensing
    journal, September 2018


    Prospects for electroactive and conducting framework materials
    journal, May 2019

    • Murase, Ryuichi; Ding, Bowen; Gu, Qinyi
    • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2149
    • DOI: 10.1098/rsta.2018.0226

    Redox‐Reversible 2D Metal–Organic Framework Nanosheets (MONs) Based on the Hydroquinone/Quinone Couple
    journal, February 2019

    • Maka, Vijay Kumar; Mukhopadhyay, Arindam; Jindal, Swati
    • Chemistry – A European Journal, Vol. 25, Issue 15
    • DOI: 10.1002/chem.201805188

    Emerging Multifunctional Metal-Organic Framework Materials
    journal, July 2016


    The organic-moiety-dominated Li + intercalation/deintercalation mechanism of a cobalt-based metal–organic framework
    journal, January 2016

    • Li, Chao; Hu, Xiaoshi; Lou, Xiaobing
    • Journal of Materials Chemistry A, Vol. 4, Issue 41
    • DOI: 10.1039/c6ta06413b

    Is iron unique in promoting electrical conductivity in MOFs?
    journal, January 2017

    • Sun, Lei; Hendon, Christopher H.; Park, Sarah S.
    • Chemical Science, Vol. 8, Issue 6
    • DOI: 10.1039/c7sc00647k

    Thermally Induced Valence Tautomeric Transition in a Two-Dimensional Fe-Tetraoxolene Honeycomb Network
    journal, August 2018

    • Chen, Jian; Sekine, Yoshihiro; Komatsumaru, Yuki
    • Angewandte Chemie, Vol. 130, Issue 37
    • DOI: 10.1002/ange.201807556

    Electrochemical and spectroscopic properties of a cobalt framework with (3,7)-c topology
    journal, January 2019

    • Hua, Carol; D'Alessandro, Deanna M.
    • CrystEngComm, Vol. 21, Issue 14
    • DOI: 10.1039/c9ce00050j

    Designing Kitaev Spin Liquids in Metal-Organic Frameworks
    journal, August 2017


    Rational modifications of PCN-700 to induce electrical conductivity: a computational study
    journal, January 2020

    • Chong, Sanggyu; Kim, Jihan
    • Dalton Transactions, Vol. 49, Issue 1
    • DOI: 10.1039/c9dt03865e

    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
    • DOI: 10.1071/ch19193

    Thermal expansion and magnetic properties of benzoquinone-bridged dinuclear rare-earth complexes
    journal, January 2017

    • Moilanen, Jani O.; Mansikkamäki, Akseli; Lahtinen, Manu
    • Dalton Trans., Vol. 46, Issue 39
    • DOI: 10.1039/c7dt02565c

    A coronene-based semiconducting two-dimensional metal-organic framework with ferromagnetic behavior
    journal, July 2018


    Zinc and cadmium complexes based on bis-(1H-tetrazol-5-ylmethyl/ylethyl)-amine ligands: structures and photoluminescence properties
    journal, January 2016

    • Wang, Duo-Zhi; Fan, Jian-Zhong; Jia, Dianzeng
    • CrystEngComm, Vol. 18, Issue 35
    • DOI: 10.1039/c6ce01311b

    An overview of different strategies to introduce conductivity in metal–organic frameworks and miscellaneous applications thereof
    journal, January 2018

    • Bhardwaj, Sanjeev K.; Bhardwaj, Neha; Kaur, Rajnish
    • Journal of Materials Chemistry A, Vol. 6, Issue 31
    • DOI: 10.1039/c8ta04220a

    Thermally Induced Valence Tautomeric Transition in a Two-Dimensional Fe-Tetraoxolene Honeycomb Network
    journal, August 2018

    • Chen, Jian; Sekine, Yoshihiro; Komatsumaru, Yuki
    • Angewandte Chemie International Edition, Vol. 57, Issue 37
    • DOI: 10.1002/anie.201807556

    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
    • DOI: 10.1039/c9sc04381k

    A Dicobalt Complex with an Unsymmetrical Quinonoid Bridge Isolated in Three Units of Charge: A Combined Structural, (Spectro)electrochemical, Magnetic and Spectroscopic Study
    journal, August 2016

    • van der Meer, Margarethe; Rechkemmer, Yvonne; Frank, Uta
    • Chemistry - A European Journal, Vol. 22, Issue 39
    • DOI: 10.1002/chem.201601579

    Recent Development and Application of Conductive MOFs
    journal, August 2018


    The role of redox hopping in metal–organic framework electrocatalysis
    journal, January 2018

    • Lin, Shaoyang; Usov, Pavel M.; Morris, Amanda J.
    • Chemical Communications, Vol. 54, Issue 51
    • DOI: 10.1039/c8cc01664j

    MOF Thin Film-Coated Metal Oxide Nanowire Array: Significantly Improved Chemiresistor Sensor Performance
    journal, May 2016

    • Yao, Ming-Shui; Tang, Wen-Xiang; Wang, Guan-E
    • Advanced Materials, Vol. 28, Issue 26
    • DOI: 10.1002/adma.201506457

    A Dual‐Ligand Porous Coordination Polymer Chemiresistor with Modulated Conductivity and Porosity
    journal, November 2019

    • Yao, Ming‐Shui; Zheng, Jia‐Jia; Wu, Ai‐Qian
    • Angewandte Chemie, Vol. 132, Issue 1
    • DOI: 10.1002/ange.201909096

    Exploiting redox activity in metal–organic frameworks: concepts, trends and perspectives
    journal, January 2016


    [Ln 16 ] complexes (Ln = Gd III , Dy III ): molecular analogues of natural minerals such as hydrotalcite
    journal, January 2018

    • Richardson, Paul; Hsu, Ting-Jung; Kuo, Che-Jung
    • Dalton Transactions, Vol. 47, Issue 37
    • DOI: 10.1039/c8dt02609b

    Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry
    journal, September 2018

    • Pedersen, Kasper S.; Perlepe, Panagiota; Aubrey, Michael L.
    • Nature Chemistry, Vol. 10, Issue 10
    • DOI: 10.1038/s41557-018-0107-7

    Chiral heterobimetallic chains from a dicyanideferrite building block including a π-conjugated TTF annulated ligand
    journal, January 2016

    • Cui, Long; Lv, Zhong-Peng; Leong, Chanel F.
    • Dalton Transactions, Vol. 45, Issue 42
    • DOI: 10.1039/c6dt01756h

    Emerging crystalline porous materials as a multifunctional platform for electrochemical energy storage
    journal, January 2017

    • Zhou, Junwen; Wang, Bo
    • Chemical Society Reviews, Vol. 46, Issue 22
    • DOI: 10.1039/c7cs00283a

    On/off switchable electronic conduction in intercalated metal-organic frameworks
    journal, August 2017

    • Ogihara, Nobuhiro; Ohba, Nobuko; Kishida, Yoshihiro
    • Science Advances, Vol. 3, Issue 8
    • DOI: 10.1126/sciadv.1603103

    High-mobility band-like charge transport in a semiconducting two-dimensional metal–organic framework
    journal, October 2018


    2D-metal–organic coordination polymers of lanthanides (La( iii ), Pr( iii ) and Nd( iii )) with redox-active dioxolene bridging ligands
    journal, January 2020

    • Kharitonov, Alexandr D.; Trofimova, Olesya Y.; Meshcheryakova, Irina N.
    • CrystEngComm, Vol. 22, Issue 28
    • DOI: 10.1039/d0ce00767f

    An updated roadmap for the integration of metal–organic frameworks with electronic devices and chemical sensors
    journal, January 2017

    • Stassen, Ivo; Burtch, Nicholas; Talin, Alec
    • Chemical Society Reviews, Vol. 46, Issue 11
    • DOI: 10.1039/c7cs00122c

    An Organic Mixed-Valence Ligand for Multistate Redox-Active Coordination Networks
    journal, March 2018

    • Ha, Joo Yeon; Koo, Jin Young; Ohtsu, Hiroyoshi
    • Angewandte Chemie International Edition, Vol. 57, Issue 17
    • DOI: 10.1002/anie.201713035

    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
    • DOI: 10.1039/c9sc00606k

    Isovalent Ag III /Ag III , Ag II /Ag II , Mixed-Valent Ag II /Ag III , and Corrolato-Based Mixed-Valency in β,β′-Linked [Bis{corrolato-silver}] n Complexes
    journal, September 2017

    • Patra, Bratati; Sobottka, Sebastian; Sinha, Woormileela
    • Chemistry - A European Journal, Vol. 23, Issue 56
    • DOI: 10.1002/chem.201703512

    The role of reticular chemistry in the design of CO2 reduction catalysts
    journal, February 2018


    Tuning the iron redox state inside a microporous porphyrinic metal organic framework
    journal, January 2017

    • Abeykoon, Brian; Grenèche, Jean-Marc; Jeanneau, Erwann
    • Dalton Transactions, Vol. 46, Issue 2
    • DOI: 10.1039/c6dt04208b

    Strong antiferromagnetic coupling of the cobalt( ii )–semiquinone radical in a dinuclear complex with 2,2′-bipyrimidine ligands
    journal, January 2020

    • Wang, Jin-Hua; Dai, Jing-Wei; Li, Zhao-Yang
    • New Journal of Chemistry
    • DOI: 10.1039/d0nj00767f

    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
    • DOI: 10.1002/chem.201805600

    Novel semiconducting iron–quinizarin metal–organic framework for application in supercapacitors
    journal, August 2019


    On‐surface Synthesis of a Semiconducting 2D Metal–Organic Framework Cu 3 (C 6 O 6 ) Exhibiting Dispersive Electronic Bands
    journal, February 2020

    • Zhang, Ran; Liu, Jing; Gao, Yifan
    • Angewandte Chemie International Edition, Vol. 59, Issue 7
    • DOI: 10.1002/anie.201913698

    A Two-Dimensional Coordination Polymer Based on 1,1':4',1''-Terphenyl-2',4,4'',5'-tetracarboxylate
    journal, May 2018


    A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity
    journal, January 2020

    • Jiang, Qiang; Xiong, Peixun; Liu, Jingjuan
    • Angewandte Chemie, Vol. 132, Issue 13
    • DOI: 10.1002/ange.201914395

    A semiconducting layered metal-organic framework magnet
    journal, July 2019


    Inter-ligand electronic coupling mediated through a dimetal bridge: dependence on metal ions and ancillary ligands
    journal, January 2017

    • Majumdar, Moumita; Saha, Sayantani; Dutta, Indranil
    • Dalton Transactions, Vol. 46, Issue 17
    • DOI: 10.1039/c6dt04679g

    Counter‐Anion‐Regulated Mixed‐Valency of Cobalt(II/III) Centers in a Metallosupramolecular Framework
    journal, July 2019

    • Hashimoto, Akari; Yoshinari, Nobuto; Nakano, Motohiro
    • Chemistry – An Asian Journal, Vol. 14, Issue 22
    • DOI: 10.1002/asia.201900743

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.