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Title: A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior

Abstract

The bifunctional salt [Co(terpy)2](TCNQ)3·CH3CN (terpy = 2,2';6',2"-terpyridine, TCNQ = 7,7,8,8-tetracyanoquino-dimethane) exhibits a high room temperature conductivity of 0.13 S cm-1 and an anomaly in conductivity at ~190 K as evidenced by variable temperature structural, magnetic and conductivity studies. The anomaly in the conductivity at 190 K has been correlated with the temperature dependent structural breathing and Jahn–Teller distortion of the low spin state of the SCO units, as well as the charge fluctuations and supramolecular π-stacking interactions of partially charged TCNQ radicals. Finally, the modular synthetic approach leads to an accessible source of partially charged TCNQ radicals for the facile preparation of bifunctional molecular materials with high electrical conductivity.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [2];  [1]; ORCiD logo [1]
  1. Texas A&M Univ., College Station, TX (United States). Dept. of Chemistry
  2. Shanghai Univ., Shanghai (China). Dept. of Chemistry, Innovative Drug Research Center
Publication Date:
Research Org.:
Texas A&M Univ., College Station, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1467560
Grant/Contract Number:  
SC0012582
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 2; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Xuan, Wang, Zhao-Xi, Xie, Haomiao, Li, Ming-Xing, Woods, Toby J., and Dunbar, Kim R. A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior. United States: N. p., 2015. Web. doi:10.1039/c5sc03547c.
Zhang, Xuan, Wang, Zhao-Xi, Xie, Haomiao, Li, Ming-Xing, Woods, Toby J., & Dunbar, Kim R. A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior. United States. https://doi.org/10.1039/c5sc03547c
Zhang, Xuan, Wang, Zhao-Xi, Xie, Haomiao, Li, Ming-Xing, Woods, Toby J., and Dunbar, Kim R. Tue . "A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior". United States. https://doi.org/10.1039/c5sc03547c. https://www.osti.gov/servlets/purl/1467560.
@article{osti_1467560,
title = {A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior},
author = {Zhang, Xuan and Wang, Zhao-Xi and Xie, Haomiao and Li, Ming-Xing and Woods, Toby J. and Dunbar, Kim R.},
abstractNote = {The bifunctional salt [Co(terpy)2](TCNQ)3·CH3CN (terpy = 2,2';6',2"-terpyridine, TCNQ = 7,7,8,8-tetracyanoquino-dimethane) exhibits a high room temperature conductivity of 0.13 S cm-1 and an anomaly in conductivity at ~190 K as evidenced by variable temperature structural, magnetic and conductivity studies. The anomaly in the conductivity at 190 K has been correlated with the temperature dependent structural breathing and Jahn–Teller distortion of the low spin state of the SCO units, as well as the charge fluctuations and supramolecular π-stacking interactions of partially charged TCNQ radicals. Finally, the modular synthetic approach leads to an accessible source of partially charged TCNQ radicals for the facile preparation of bifunctional molecular materials with high electrical conductivity.},
doi = {10.1039/c5sc03547c},
journal = {Chemical Science},
number = 2,
volume = 7,
place = {United States},
year = {2015},
month = {12}
}

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Works referenced in this record:

Hybrid organic–inorganic materials: a land of multidisciplinarity
journal, January 1996

  • Judeinstein, Patrick; Sanchez, Clément
  • J. Mater. Chem., Vol. 6, Issue 4
  • DOI: 10.1039/JM9960600511

Design and synthesis of organic metals
journal, July 1974

  • Garito, Anthony F.; Heeger, Alan J.
  • Accounts of Chemical Research, Vol. 7, Issue 7
  • DOI: 10.1021/ar50079a004

Highly Conducting Coordination Polymers Based on Infinite M(4,4′-bpy) Chains Flanked by Regular Stacks of Non-Integer TCNQ Radicals
journal, August 2011

  • Ballesteros-Rivas, Maria; Ota, Akira; Reinheimer, Eric
  • Angewandte Chemie International Edition, Vol. 50, Issue 41
  • DOI: 10.1002/anie.201101658

Synergistic electrical bistability in a conductive spin crossover heterostructure
journal, January 2015

  • Chen, Yan-Cong; Meng, Yan; Ni, Zhao-Ping
  • Journal of Materials Chemistry C, Vol. 3, Issue 5
  • DOI: 10.1039/C4TC02580F

Multifunctional molecular materials
journal, June 2003


Electrical properties and phase transitions of trimethylammonium-iodine-tetracyanoquinodimethane (TMA-I-TCNQ)
journal, October 1983


Modified Chesnut Model for Spin-Crossover Semiconductors [Fe(acpa) 2 ](TCNQ) n
journal, January 2002

  • Nakano, Motohiro; Fujita, Naoki; Matsubayashi, Gen-Etsu
  • Molecular Crystals and Liquid Crystals, Vol. 379, Issue 1
  • DOI: 10.1080/713738669

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

Complex TCNQ salts with asymmetric donors. I. Transport properties
journal, December 1978


Organic/Inorganic Hybrid Materials: Challenges for ab Initio Methodology
journal, August 2014

  • Draxl, Claudia; Nabok, Dmitrii; Hannewald, Karsten
  • Accounts of Chemical Research, Vol. 47, Issue 11
  • DOI: 10.1021/ar500096q

An unusual discontinuity in the thermal spin transition in [Co(terpy)2][BF4]2
journal, January 2010

  • Kilner, Colin A.; Halcrow, Malcolm A.
  • Dalton Transactions, Vol. 39, Issue 38
  • DOI: 10.1039/c0dt00295j

Structural and Physical Properties of a Series of 7,7,8,8-Tetracyanoquinodimethane Salts with Dications Bearing Two Terminal Pyridinium Rings
journal, September 2014

  • Kubota, Hiroyuki; Takahashi, Yukihiro; Harada, Jun
  • Crystal Growth & Design, Vol. 14, Issue 11
  • DOI: 10.1021/cg500820v

Photomagnetic Response in Highly Conductive Iron(II) Spin-Crossover Complexes with TCNQ Radicals
journal, November 2014

  • Phan, Hoa; Benjamin, Shermane M.; Steven, Eden
  • Angewandte Chemie International Edition, Vol. 54, Issue 3
  • DOI: 10.1002/anie.201408680

Measurement of Seebeck and Hall effects in compactions of TCNQ salts
journal, January 1971

  • Blythe, A. R.; Boon, M. R.; Wright, P. G.
  • Discussions of the Faraday Society, Vol. 51
  • DOI: 10.1039/df9715100110

Spin-crossover behavior and electrical conduction property in iron( ii ) complexes with tetrathiafulvalene moieties
journal, January 2011

  • Nihei, Masayuki; Takahashi, Nobukazu; Nishikawa, Hiroyuki
  • Dalton Trans., Vol. 40, Issue 10
  • DOI: 10.1039/C0DT01092H

Synthesis and Properties of Cobalt(III) Complexes of 4-Substituted Pyridine-Capped Dioxocyclams
journal, December 2005

  • Reiff, Angela L.; Garcia-Frutos, Eva M.; Gil, Jun Mo
  • Inorganic Chemistry, Vol. 44, Issue 25
  • DOI: 10.1021/ic050200h

Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors
journal, October 1999


Spin Crossover Probes Confer Multistability to Organic Conducting Polymers
journal, September 2014

  • Koo, Yong-Sung; Galán-Mascarós, José Ramón
  • Advanced Materials, Vol. 26, Issue 39
  • DOI: 10.1002/adma.201402579

High-spin-low-spin equilibriums of cobalt(2+) in the terpyridine complexes Co(terpy)2X2.nH2O
journal, August 1982

  • Kremer, S.; Henke, W.; Reinen, D.
  • Inorganic Chemistry, Vol. 21, Issue 8
  • DOI: 10.1021/ic00138a019

Single-Chain Magnetic Behavior in a Hetero-Tri-Spin Complex Mediated by Supramolecular Interactions with TCNQF .− Radicals
journal, September 2014

  • Wang, Zhao-Xi; Zhang, Xuan; Zhang, Yuan-Zhu
  • Angewandte Chemie International Edition, Vol. 53, Issue 43
  • DOI: 10.1002/anie.201407628

A cadmium TCNQ-based semiconductor with versatile binding modes and non-integer redox states
journal, January 2014

  • Zhang, Xuan; Zhang, Zhongyue; Zhao, Hanhua
  • Chem. Commun., Vol. 50, Issue 12
  • DOI: 10.1039/C3CC48330D

Iron(II) complexes of 2,6-di(pyrazol-1-yl)pyridines—A versatile system for spin-crossover research
journal, November 2009


Long-range magnetic order in a purely organic 2D layer adsorbed on epitaxial graphene
journal, April 2013

  • Garnica, Manuela; Stradi, Daniele; Barja, Sara
  • Nature Physics, Vol. 9, Issue 6
  • DOI: 10.1038/nphys2610

Structure of the red, semiconducting form of 4,4',5,5'-tetramethyl-Δ 2,2' -bi-1,3-diselenole-7,7,8,8-tetracyano- p -quinodimethane, TMTSF–TCNQ
journal, April 1982

  • Kistenmacher, T. J.; Emge, T. J.; Bloch, A. N.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 4
  • DOI: 10.1107/S0567740882005275

Vanadium 7,7,8,8-Tetracyano- p -quinodimethane (V[TCNQ] 2 )-Based Magnets
journal, October 2004

  • Vickers, Elaine B.; Selby, Trent D.; Thorum, Matthew S.
  • Inorganic Chemistry, Vol. 43, Issue 20
  • DOI: 10.1021/ic049552z

A one-dimensional coordination polymer exhibiting simultaneous spin-crossover and semiconductor behaviour
journal, January 2011

  • Xue, Wei; Wang, Bao-Ying; Zhu, Jie
  • Chemical Communications, Vol. 47, Issue 37
  • DOI: 10.1039/c1cc12852c

Superconducting fluctuations and the peierls instability in an organic solid
journal, June 1973


Single-chain magnets: beyond the Glauber model
journal, January 2013

  • Zhang, Wei-Xiong; Ishikawa, Ryuta; Breedlove, Brian
  • RSC Advances, Vol. 3, Issue 12
  • DOI: 10.1039/c2ra22675h

[Fe(sal2-trien)][Ni(dmit)2]: towards switchable spin crossover molecular conductors
journal, January 2005

  • Dorbes, St�phane; Valade, Lydie; Real, Jos� A.
  • Chemical Communications, Issue 1
  • DOI: 10.1039/b412182a

Electrical Conductivity and Spin Crossover:  A New Achievement with a Metal Bis Dithiolene Complex
journal, October 2007

  • Faulmann, Christophe; Jacob, Kane; Dorbes, Stéphane
  • Inorganic Chemistry, Vol. 46, Issue 21
  • DOI: 10.1021/ic062461c

Coexistence of ferromagnetism and metallic conductivity in a molecule-based layered compound
journal, November 2000

  • Coronado, Eugenio; Galán-Mascarós, José R.; Gómez-García, Carlos J.
  • Nature, Vol. 408, Issue 6811
  • DOI: 10.1038/35044035

Electrical Conductivity Modulation Coupled to a High-Spin−Low-Spin Conversion in the Molecular System [Fe III (qsal) 2 ][Ni(dmit) 2 ] 3 ·CH 3 CN·H 2 O
journal, July 2006

  • Takahashi, Kazuyuki; Cui, Heng-Bo; Okano, Yoshinori
  • Inorganic Chemistry, Vol. 45, Issue 15
  • DOI: 10.1021/ic060852l

Single-Molecule Magnets
journal, November 2000

  • Christou, George; Gatteschi, Dante; Hendrickson, David N.
  • MRS Bulletin, Vol. 25, Issue 11
  • DOI: 10.1557/mrs2000.226

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

Spin state switching in iron coordination compounds
journal, January 2013

  • Gütlich, Philipp; Gaspar, Ana B.; Garcia, Yann
  • Beilstein Journal of Organic Chemistry, Vol. 9
  • DOI: 10.3762/bjoc.9.39

Carrier Concentration Dependent Conduction in Insulator-Doped Donor/Acceptor Chain Compounds
journal, November 2013

  • Nishio, Masaki; Hoshino, Norihisa; Kosaka, Wataru
  • Journal of the American Chemical Society, Vol. 135, Issue 47
  • DOI: 10.1021/ja409785a

Spin Crossover - Quo Vadis?
journal, February 2013


Structural distortions of the spin-crossover material [Co(pyterpy) 2 ](TCNQ) 2 mediated by supramolecular interactions
journal, January 2015

  • Zhang, Xuan; Xie, Haomiao; Ballesteros-Rivas, Maria
  • Journal of Materials Chemistry C, Vol. 3, Issue 36
  • DOI: 10.1039/C5TC01851J

Spontaneous Multielectron Transfer from the Surfaces of PbS Quantum Dots to Tetracyanoquinodimethane
journal, May 2013

  • Knowles, Kathryn E.; Malicki, Michał; Parameswaran, Radha
  • Journal of the American Chemical Society, Vol. 135, Issue 19
  • DOI: 10.1021/ja4003074

The first coordination compound containing three different types of spin carriers: 2p–3d–4f (TCNQ˙–, Cu2+ and Gd3+)
journal, June 2002

  • Madalan, Augustin M.; Roesky, Herbert W.; Andruh, Marius
  • Chemical Communications, Issue 15
  • DOI: 10.1039/b202628g

Organic Conductors with Unusual Band Fillings
journal, November 2004


Substituted Quinodimethans. II. Anion-radical Derivatives and Complexes of 7,7,8,8-Tetracyanoquinodimethan
journal, September 1962

  • Melby, L. R.; Harder, R. J.; Hertler, W. R.
  • Journal of the American Chemical Society, Vol. 84, Issue 17
  • DOI: 10.1021/ja00876a029

Molecular/Organic Ferromagnets
journal, April 1988


Hybrid CuTCNQ/AgTCNQ Metal-Organic Charge Transfer Complexes via Galvanic Replacement vs Corrosion-Recrystallization
journal, October 2014

  • Pearson, Andrew; Ramanathan, Rajesh; O'Mullane, Anthony P.
  • Advanced Functional Materials, Vol. 24, Issue 48
  • DOI: 10.1002/adfm.201402320

A new metal–organic hybrid material with intrinsic resistance-based bistability: monitoring in situ room temperature switching behavior
journal, January 2014

  • Zhang, Zhongyue; Zhao, Hanhua; Matsushita, Michio M.
  • J. Mater. Chem. C, Vol. 2, Issue 2
  • DOI: 10.1039/C3TC31577K

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

Magnetic ordering in TCNQ-based metal–organic frameworks with host–guest interactions
journal, January 2015

  • Zhang, Xuan; Saber, Mohamed R.; Prosvirin, Andrey P.
  • Inorganic Chemistry Frontiers, Vol. 2, Issue 10
  • DOI: 10.1039/C5QI00128E

Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds
journal, September 1999


Evidence of the Chemical Uniaxial Strain Effect on Electrical Conductivity in the Spin-Crossover Conducting Molecular System: [Fe III (qnal) 2 ][Pd(dmit) 2 ] 5 ·Acetone
journal, May 2008

  • Takahashi, Kazuyuki; Cui, Heng-Bo; Okano, Yoshinori
  • Journal of the American Chemical Society, Vol. 130, Issue 21
  • DOI: 10.1021/ja801585r

Inorganic/Organic Hybrid Materials
journal, October 1998


Magnetically ordered molecule-based materials
journal, January 2011


The foundation of modern spin-crossover
journal, January 2013


Spin-crossover in cobalt(II) compounds containing terpyridine and its derivatives
journal, September 2011

  • Hayami, Shinya; Komatsu, Yasuka; Shimizu, Tetsuya
  • Coordination Chemistry Reviews, Vol. 255, Issue 17-18
  • DOI: 10.1016/j.ccr.2011.05.016

Soft porous crystal meets TCNQ: charge transfer-type porous coordination polymers
journal, January 2011

  • Shimomura, Satoru; Kitagawa, Susumu
  • Journal of Materials Chemistry, Vol. 21, Issue 15
  • DOI: 10.1039/c1jm10208g

Electrochemical and photochemical routes to semiconducting transition metal-tetracyanoquinodimethane coordination polymers
journal, June 2014

  • Nafady, Ayman; O’Mullane, Anthony P.; Bond, Alan M.
  • Coordination Chemistry Reviews, Vol. 268
  • DOI: 10.1016/j.ccr.2014.01.017

Highly Conducting Coordination Polymers Based on Infinite M(4,4′-bpy) Chains Flanked by Regular Stacks of Non-Integer TCNQ Radicals
journal, August 2011

  • Ballesteros-Rivas, Maria; Ota, Akira; Reinheimer, Eric
  • Angewandte Chemie, Vol. 123, Issue 41
  • DOI: 10.1002/ange.201101658

Organic Conductors with Unusual Band Fillings
journal, February 2005


Magnetically Ordered Molecule-Based Materials
journal, July 2007


Photomagnetic Response in Highly Conductive Iron(II) Spin-Crossover Complexes with TCNQ Radicals
journal, November 2014

  • Phan, Hoa; Benjamin, Shermane M.; Steven, Eden
  • Angewandte Chemie, Vol. 127, Issue 3
  • DOI: 10.1002/ange.201408680

Single-Molecule Magnets
journal, May 2000

  • Ruiz-molina, Daniel; Christou, George; Hendrickson, David N.
  • Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol. 343, Issue 1
  • DOI: 10.1080/10587250008023497

Superconducting fluctuations and the Peierls instability in an organic solid
journal, December 1993


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Conducting Molecular Nanomagnet of Dy III with Partially Charged TCNQ Radicals
journal, May 2017

  • Zhang, Xuan; Xie, Haomiao; Ballesteros-Rivas, Maria
  • Chemistry - A European Journal, Vol. 23, Issue 31
  • DOI: 10.1002/chem.201701590

Pancake Bonding in π-Stacked Trimers in a Salt of Tetrachloroquinone Anion
journal, May 2018

  • Molčanov, Krešimir; Mou, Zhongyu; Kertesz, Miklos
  • Chemistry - A European Journal, Vol. 24, Issue 33
  • DOI: 10.1002/chem.201800672

Pancake Bonding: An Unusual Pi-Stacking Interaction
journal, November 2018


Sliding Polymeric Layers and Anion Displacement Coupled with Spin Crossover in Two-Dimensional Networks of [Fe(hbtz) 2 (CH 3 CN) 2 ](BF 4 ) 2
journal, January 2019

  • Książek, Maria; Weselski, Marek; Ilczyszyn, Maria
  • Chemistry - A European Journal, Vol. 25, Issue 9
  • DOI: 10.1002/chem.201804721

Towards Dual-Functionality Spin-Crossover Complexes
journal, January 2018

  • Feltham, Humphrey L. C.; Dankhoff, Katja; Meledandri, Carla J.
  • ChemPlusChem, Vol. 83, Issue 7
  • DOI: 10.1002/cplu.201700512

Use of the TCNQF 4 2− Dianion in the Spontaneous Redox Formation of [Fe III (L ) 2 ][TCNQF 4 ⋅− ]
journal, March 2018


Structural diversity and magnetic properties of six cobalt coordination polymers based on 2,2′-phosphinico-dibenzoate ligand
journal, January 2016

  • Wang, Zhao-Xi; Wu, Lin-Fei; Zhang, Xuan
  • Dalton Transactions, Vol. 45, Issue 48
  • DOI: 10.1039/c6dt04010a

Solvent-tuned charge-transfer properties of chiral Pt( ii ) complex and TCNQ˙ anion adducts
journal, January 2018

  • Zhang, Xiao-Peng; Wang, Li-Li; Zhang, Da-Shuai
  • RSC Advances, Vol. 8, Issue 20
  • DOI: 10.1039/c8ra01330f

Bistable molecular materials with dynamic structures
journal, January 2020

  • Yao, Zi-Shuo; Tang, Zheng; Tao, Jun
  • Chemical Communications, Vol. 56, Issue 14
  • DOI: 10.1039/c9cc09238b

Synthesis, structure and magnetic properties of copper( ii ) azide
journal, January 2019

  • Shi, Taqing; Xu, Ye; Zou, Ya-Jing
  • Dalton Transactions, Vol. 48, Issue 30
  • DOI: 10.1039/c9dt01450k

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

Towards understanding π-stacking interactions between non-aromatic rings
journal, February 2019


Spin-Singlet Transition in the Magnetic Hybrid Compound from a Spin-Crossover Fe(III) Cation and π-Radical Anion
journal, August 2017