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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. doi: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 = {Tue Nov 17 00:00:00 EST 2015},
month = {Tue Nov 17 00:00:00 EST 2015}
}

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Cited by: 273 works
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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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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

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, Vol. 129, Issue 52
  • DOI: 10.1002/ange.201709558

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

  • Ha, Joo Yeon; Koo, Jin Young; Ohtsu, Hiroyoshi
  • Angewandte Chemie, Vol. 130, Issue 17
  • DOI: 10.1002/ange.201713035

Titelbild: A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity (Angew. Chem. 13/2020)
journal, January 2020

  • Jiang, Qiang; Xiong, Peixun; Liu, Jingjuan
  • Angewandte Chemie, Vol. 132, Issue 13
  • DOI: 10.1002/ange.202001277

Cover Picture: A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity (Angew. Chem. Int. Ed. 13/2020)
journal, March 2020

  • Jiang, Qiang; Xiong, Peixun; Liu, Jingjuan
  • Angewandte Chemie International Edition, Vol. 59, Issue 13
  • DOI: 10.1002/anie.202001277

Two-Dimensional Nanosheets from Redox-Active Superatoms
journal, August 2017


Breathing-Dependent Redox Activity in a Tetrathiafulvalene-Based Metal–Organic Framework
journal, July 2018

  • Souto, Manuel; Romero, Jorge; Calbo, Joaquín
  • Journal of the American Chemical Society, Vol. 140, Issue 33
  • DOI: 10.1021/jacs.8b05890

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


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

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

Metal–Organic Framework Co-MOF-74-Based Host–Guest Composites for Resistive Gas Sensing
text, January 2019

  • Strauss, Ina; Mundstock, Alexander; Treger, Marvin
  • Washington D.C. : American Chemical Society
  • DOI: 10.15488/9172

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