TY - JOUR
T1 - Heterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet
AU - Shen, Yongbing
AU - Cui, Mengxing
AU - Takaishi, Shinya
AU - Kawasoko, Hideyuki
AU - Sugimoto, Kunihisa
AU - Tsumuraya, Takao
AU - Otsuka, Akihiro
AU - Kwon, Eunsang
AU - Yoshida, Takefumi
AU - Hoshino, Norihisa
AU - Kawachi, Kazuhiko
AU - Kasama, Yasuhiko
AU - Akutagawa, Tomoyuki
AU - Fukumura, Tomoteru
AU - Yamashita, Masahiro
N1 - Funding Information:
This work was supported by JSPS KAKENHI Grant Numbers JP19H05631 (S.T. and M.Y.). M.Y. acknowledges the support of the 111 Project (B18030) from China. Computations were carried out using the computer resources offered under the category of the Trial Use Project by the Research Institute for Information Technology, Kyushu University.
Publisher Copyright:
© 2022, The Author(s).
PY - 2022/12
Y1 - 2022/12
N2 - Lithium-ion-encapsulated fullerenes (Li+@C60) are 3D superatoms with rich oxidative states. Here we show a conductive and magnetically frustrated metal–fullerene-bonded framework {[Cu4(Li@C60)(L)(py)4](NTf2)(hexane)}n (1) (L = 1,2,4,5-tetrakis(methanesulfonamido)benzene, py = pyridine, NTf2− = bis(trifluoromethane)sulfonamide anion) prepared from redox-active dinuclear metal complex Cu2(L)(py)4 and lithium-ion-encapsulated fullerene salt (Li+@C60)(NTf2−). Electron donor Cu2(L)(py)2 bonds to acceptor Li+@C60 via eight Cu‒C bonds. Cu–C bond formation stems from spontaneous charge transfer (CT) between Cu2(L)(py)4 and (Li+@C60)(NTf2−) by removing the two-terminal py molecules, yielding triplet ground state [Cu2(L)(py)2]+(Li+@C60•−), evidenced by absorption and electron paramagnetic resonance (EPR) spectra, magnetic properties and quantum chemical calculations. Moreover, Li+@C60•− radicals (S = ½) and Cu2+ ions (S = ½) interact antiferromagnetically in triangular spin lattices in the absence of long-range magnetic ordering to 1.8 K. The low-temperature heat capacity indicated that compound 1 is a potential candidate for an S = ½ quantum spin liquid (QSL).
AB - Lithium-ion-encapsulated fullerenes (Li+@C60) are 3D superatoms with rich oxidative states. Here we show a conductive and magnetically frustrated metal–fullerene-bonded framework {[Cu4(Li@C60)(L)(py)4](NTf2)(hexane)}n (1) (L = 1,2,4,5-tetrakis(methanesulfonamido)benzene, py = pyridine, NTf2− = bis(trifluoromethane)sulfonamide anion) prepared from redox-active dinuclear metal complex Cu2(L)(py)4 and lithium-ion-encapsulated fullerene salt (Li+@C60)(NTf2−). Electron donor Cu2(L)(py)2 bonds to acceptor Li+@C60 via eight Cu‒C bonds. Cu–C bond formation stems from spontaneous charge transfer (CT) between Cu2(L)(py)4 and (Li+@C60)(NTf2−) by removing the two-terminal py molecules, yielding triplet ground state [Cu2(L)(py)2]+(Li+@C60•−), evidenced by absorption and electron paramagnetic resonance (EPR) spectra, magnetic properties and quantum chemical calculations. Moreover, Li+@C60•− radicals (S = ½) and Cu2+ ions (S = ½) interact antiferromagnetically in triangular spin lattices in the absence of long-range magnetic ordering to 1.8 K. The low-temperature heat capacity indicated that compound 1 is a potential candidate for an S = ½ quantum spin liquid (QSL).
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U2 - 10.1038/s41467-022-28134-w
DO - 10.1038/s41467-022-28134-w
M3 - Article
C2 - 35078998
AN - SCOPUS:85123484513
SN - 2041-1723
VL - 13
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 495
ER -