An Organic–Inorganic Hybrid Exhibiting Electrical Conduction and Single-Ion Magnetism
Corresponding Author
Dr. Yongbing Shen
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
Search for more papers by this authorCorresponding Author
Dr. Goulven Cosquer
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
Present address: Research Group of Solid Material Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashihiroshima, Hiroshima, 739-8526 Japan
Search for more papers by this authorProf. Hiroshi Ito
Department of Applied Physics, Nagoya University, Chikusa-ku, Nagoya, 464-603 Japan
Search for more papers by this authorDr. David C. Izuogu
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK
Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, 410001 Enugu State, Nigeria
Search for more papers by this authorProf. Alex J. W. Thom
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK
Search for more papers by this authorDr. Toshiaki Ina
Research & Utilization Division (Japan) Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Sayou-gun, Hyogo, 679-5198 Japan
Search for more papers by this authorDr. Tomoya Uruga
Research & Utilization Division (Japan) Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Sayou-gun, Hyogo, 679-5198 Japan
Search for more papers by this authorDr. Takefumi Yoshida
Electronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), Tsukuba, 305-0044 Japan
Search for more papers by this authorProf. Shinya Takaishi
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
Search for more papers by this authorProf. Brian K. Breedlove
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
Search for more papers by this authorDr. Zhao-Yang Li
School of Materials Science and Engineering, Nankai University, Tianjin, 300350 China
Search for more papers by this authorCorresponding Author
Prof. Masahiro Yamashita
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
School of Materials Science and Engineering, Nankai University, Tianjin, 300350 China
WPI-Advanced Institute for Materials Research (AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577 Japan
Search for more papers by this authorCorresponding Author
Dr. Yongbing Shen
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
Search for more papers by this authorCorresponding Author
Dr. Goulven Cosquer
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
Present address: Research Group of Solid Material Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashihiroshima, Hiroshima, 739-8526 Japan
Search for more papers by this authorProf. Hiroshi Ito
Department of Applied Physics, Nagoya University, Chikusa-ku, Nagoya, 464-603 Japan
Search for more papers by this authorDr. David C. Izuogu
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK
Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, 410001 Enugu State, Nigeria
Search for more papers by this authorProf. Alex J. W. Thom
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK
Search for more papers by this authorDr. Toshiaki Ina
Research & Utilization Division (Japan) Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Sayou-gun, Hyogo, 679-5198 Japan
Search for more papers by this authorDr. Tomoya Uruga
Research & Utilization Division (Japan) Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Sayou-gun, Hyogo, 679-5198 Japan
Search for more papers by this authorDr. Takefumi Yoshida
Electronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), Tsukuba, 305-0044 Japan
Search for more papers by this authorProf. Shinya Takaishi
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
Search for more papers by this authorProf. Brian K. Breedlove
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
Search for more papers by this authorDr. Zhao-Yang Li
School of Materials Science and Engineering, Nankai University, Tianjin, 300350 China
Search for more papers by this authorCorresponding Author
Prof. Masahiro Yamashita
Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578 Sendai, Japan
School of Materials Science and Engineering, Nankai University, Tianjin, 300350 China
WPI-Advanced Institute for Materials Research (AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577 Japan
Search for more papers by this authorGraphical Abstract
Magnetic personality: Electrocrystallisation of tetrathiafulvalene (TTF) and the magnetic precursor [Co(pdms)2] (H2pdms=1,2-bis(methanesulfonamido)benzene) afforded a 3D conducting single-ion magnet. Multiple charge-transfer interactions between the components produce partial oxidation states for TTF, the Co ion, and the pdms ligand, allowing electrical conductivity at low temperatures.
Abstract
The first three-dimensional (3D) conductive single-ion magnet (SIM), (TTF)2[Co(pdms)2] (TTF=tetrathiafulvalene and H2pdms=1,2-bis(methanesulfonamido)benzene), was electrochemically synthesised and investigated structurally, physically, and theoretically. The similar oxidation potentials of neutral TTF and the molecular precursor [HNEt3]2[M(pdms)2] (M=Co, Zn) allow for multiple charge transfers (CTs) between the SIM donor [M(pdms)2]n− and the TTF.+ acceptor, as well as an intradonor CT from the pdms ligand to Co ion upon electrocrystallisation. Usually TTF functions as a donor, whereas in our system TTF is both a donor and an accepter because of the similar oxidation potentials. Furthermore, the [M(pdms)2]n− donor and TTF.+ acceptor are not segregated but strongly interact with each other, contrary to reported layered donor–acceptor electrical conductors. The strong intermolecular and intramolecular interactions, combined with CT, allow for relatively high electrical conductivity even down to very low temperatures. Furthermore, SIM behaviour with slow magnetic relaxation and opening of hysteresis loops was observed. (TTF)2[Co(pdms)2] (2-Co) is an excellent building block for preparing new conductive SIMs.
Conflict of interest
The authors declare no conflict of interest.
Supporting Information
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