TY - JOUR
T1 - An Organic–Inorganic Hybrid Exhibiting Electrical Conduction and Single-Ion Magnetism
AU - Shen, Yongbing
AU - Cosquer, Goulven
AU - Ito, Hiroshi
AU - Izuogu, David C.
AU - Thom, Alex J.W.
AU - Ina, Toshiaki
AU - Uruga, Tomoya
AU - Yoshida, Takefumi
AU - Takaishi, Shinya
AU - Breedlove, Brian K.
AU - Li, Zhao Yang
AU - Yamashita, Masahiro
N1 - Funding Information:
This work was partially supported by CREST, JST Grant number JPMJCR12L3. M.Y. is thankful for the support of the 111 project (B18030) from China. This work was performed under the approval of the Photon Factory Program Advisory Committee (Proposal No. 2018G083, beamline NW2A.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/2/3
Y1 - 2020/2/3
N2 - 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.
AB - 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.
KW - 3D networks
KW - charge transfer
KW - crystalline solids
KW - d–pi interactions
KW - electrical conductivity
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U2 - 10.1002/anie.201910523
DO - 10.1002/anie.201910523
M3 - Article
C2 - 31782883
AN - SCOPUS:85078342996
SN - 1433-7851
VL - 59
SP - 2399
EP - 2406
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 6
ER -