An Organic-Inorganic Hybrid Exhibiting Electrical Conduction and Single-Ion Magnetism

Yongbing Shen; Goulven Cosquer; Hiroshi Ito; David C Izuogu; Alex J W Thom; Toshiaki Ina; Tomoya Uruga; Takefumi Yoshida; Shinya Takaishi; Brian K Breedlove; Zhao-Yang Li; Masahiro Yamashita

doi:10.1002/anie.201910523

An Organic-Inorganic Hybrid Exhibiting Electrical Conduction and Single-Ion Magnetism

Angew Chem Int Ed Engl. 2020 Feb 3;59(6):2399-2406. doi: 10.1002/anie.201910523. Epub 2020 Jan 21.

Authors

Yongbing Shen¹, Goulven Cosquer^{1

2}, Hiroshi Ito³, David C Izuogu^{4

5}, Alex J W Thom⁴, Toshiaki Ina⁶, Tomoya Uruga⁶, Takefumi Yoshida⁷, Shinya Takaishi¹, Brian K Breedlove¹, Zhao-Yang Li⁸, Masahiro Yamashita^{1

8

9}

Affiliations

¹ Department of Chemistry, Graduate School of Science, Tohoku University, 980-8578, Sendai, Japan.
² Present address: Research Group of Solid Material Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashihiroshima, Hiroshima, 739-8526, Japan.
³ Department of Applied Physics, Nagoya University, Chikusa-ku, Nagoya, 464-603, Japan.
⁴ Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
⁵ Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, 410001, Enugu State, Nigeria.
⁶ Research & Utilization Division (Japan) Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Sayou-gun, Hyogo, 679-5198, Japan.
⁷ Electronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), Tsukuba, 305-0044, Japan.
⁸ School of Materials Science and Engineering, Nankai University, Tianjin, 300350, China.
⁹ WPI-Advanced Institute for Materials Research (AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan.

PMID: 31782883
DOI: 10.1002/anie.201910523

Abstract

The first three-dimensional (3D) conductive single-ion magnet (SIM), (TTF)₂ [Co(pdms)₂ ] (TTF=tetrathiafulvalene and H₂ pdms=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.

Keywords: 3D networks; charge transfer; crystalline solids; d-pi interactions; electrical conductivity.

Abstract

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