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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 Fe III centers and paramagnetic semiquinoid linkers, (NBu 4) 2Fe III 2(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 Na 0.9(NBu 4) 1.8Fe III 2(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) (SC-22)
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. doi: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. doi: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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Cited by: 131 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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journal, March 2018

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

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journal, August 2018

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

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

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

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

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

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journal, July 2018


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journal, April 2019


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

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

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

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

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

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

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

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

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

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

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

[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

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

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

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

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

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journal, May 2017

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

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