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Featured researches published by Fupin Liu.


Scientific Reports | 2013

An improbable monometallic cluster entrapped in a popular fullerene cage: YCN@C(s)(6)-C82.

Shangfeng Yang; Chuanbao Chen; Fupin Liu; Yunpeng Xie; Fengyu Li; Mingzhi Jiao; Mitsuaki Suzuki; Tao Wei; Song Wang; Zhongfang Chen; Xing Lu; Takeshi Akasaka

Since the first proposal that fullerenes are capable of hosting atoms, ions, or clusters by the late Smalley in 1985, tremendous examples of endohedral metallofullerenes (EMFs) have been reported. Breaking the dogma that monometallofullerenes (mono-EMFs) always exist in the form of M@C2n while clusterfullerenes always require multiple (two to four) metal cations to stabilize a cluster that is unstable as a single moiety, here we show an unprecedented monometallic endohedral clusterfullerene entrapping an yttrium cyanide cluster inside a popular C82 cage—YCN@Cs(6)-C82. X-ray crystallography and 13C NMR characterization unambiguously determine the cage symmetry and the endohedal cyanide structure, unexpectedly revealing that the entrapped YCN cluster is triangular. The unprecedented monometallic clusterfullerene structure unveiled by YCN@Cs(6)-C82 opens up a new avenue for stabilizing a cluster by a single metal cation within a carbon cage, and will surely stimulate further studies on the stability and formation mechanism of EMFs.


Inorganic Chemistry | 2012

Titanium/yttrium mixed metal nitride clusterfullerene TiY2N@C80: synthesis, isolation, and effect of the group-III metal.

Chuanbao Chen; Fupin Liu; Shujuan Li; Nan Wang; Alexey A. Popov; Mingzhi Jiao; Tao Wei; Qunxiang Li; Lothar Dunsch; Shangfeng Yang

Titanium/yttrium mixed metal nitride clusterfullerene (MMNCF) TiY(2)N@C(80) has been successfully synthesized, representing the first Ti-containing non-scandium MMNCF. TiY(2)N@C(80) has been isolated by multistep HPLC and characterized by various spectroscopies in combination with DFT computations. The electronic absorption property of TiY(2)N@C(80) was characterized by UV-vis-NIR spectroscopy, indicating the resemblance to that of TiSc(2)N@C(80) with broad shoulder absorptions. The optical band gap of TiY(2)N@C(80) (1.39 eV) is very close to that of TiSc(2)N@C(80) (1.43 eV) but much smaller than that of Y(3)N@C(80)(I(h), 1.58 eV). Such a resemblance of the overall absorption feature of TiY(2)N@C(80) to TiSc(2)N@C(80) suggests that TiY(2)N@C(80) has a similar electronic configuration to that of TiSc(2)N@C(80), that is, (TiY(2)N)(6+)@C(80)(6-). FTIR spectroscopic study and DFT calculations accomplish the assignment of the C(80):I(h) isomer to the cage structure of TiY(2)N@C(80), with the C(1) conformer being the lowest energy structure, which is different from the C(s) conformer assigned to TiSc(2)N@C(80). The electrochemical properties of TiY(2)N@C(80) were investigated by cyclic voltammetry, revealing the reversible first oxidation and first reduction step with E(1/2) at 0.00 and -1.13 V, respectively, both of which are more negative than those of TiSc(2)N@C(80), while the electrochemical energy gap of TiY(2)N@C(80) (1.11 V) is almost the same as that of TiSc(2)N@C(80) (1.10 V). Contrary to the reversible first reduction step, the second and third reduction steps of TiY(2)N@C(80) are irreversible, and this redox behavior is dramatically different from that of TiSc(2)N@C(80), which shows three reversible reduction steps, indicating the strong influence of the encaged group-III metal (Y or Sc) on the electronic properties of TiM(2)N@C(80) (M = Y, Sc).


Journal of the American Chemical Society | 2015

Capturing the Long-Sought Small-Bandgap Endohedral Fullerene Sc3N@C82 with Low Kinetic Stability

Tao Wei; Song Wang; Fupin Liu; Yuan-Zhi Tan; Xianjun Zhu; Su-Yuan Xie; Shangfeng Yang

The long-sought small-bandgap endohedral fullerene Sc3N@C82 with low kinetic stability has been successfully synthesized and isolated for the first time, for which the molecular structure has been unambiguously determined as Sc3N@C82-C2v(39718) by single crystal X-ray diffraction. The C82-C2v(39718) (or labeled as C82-C2v(9) according to the conventional numbering of the isolated pentagon rule (IPR) isomers based on the Fowler-Monolopoulos spiral algorithm) isomeric cage of Sc3N@C82 agrees well with its most stable isomer previously predicted by DFT computations and is dramatically different to those of the reported counterparts M3N@C82-Cs(39663) (M = Gd, Y) based on a non-IPR C82 isomer, revealing the strong dependence of the cage isomeric structure on the size of the encaged metal for C82-based metal nitride clusterfullerenes (NCFs).


Inorganic Chemistry | 2014

Putting a Terbium-Monometallic Cyanide Cluster into the C82 Fullerene Cage: TbCN@C2(5)-C82

Fupin Liu; Song Wang; Jian Guan; Tao Wei; Minxiang Zeng; Shangfeng Yang

The first terbium (Tb)-monometallic cyanide clusterfullerene (CYCF), TbCN@C82, has been successfully synthesized and isolated, whose molecular structure was determined unambiguously as TbCN@C2(5)-C82 by single crystal X-ray diffraction. The C2(5)-C82 isomeric cage represents a new cage capable of encapsulating a monometallic cyanide cluster. The C-N bond length within the encaged TbCN cluster is determined to be 0.94(5) Å, which is smaller by at least 0.17 Å than those of the reported C-N triplet bonds in traditional cyanide/nitrile compounds and cyano coordination complexes. An electronic configuration of [Tb(3+)(CN)(-)](2+)@[C82](2-) was proposed for TbCN@C82.


Journal of the American Chemical Society | 2016

Entrapping a Group-VB Transition Metal, Vanadium, within an Endohedral Metallofullerene: VxSc3–xN@Ih-C80 (x = 1, 2)

Tao Wei; Song Wang; Xing Lu; Yuan-Zhi Tan; Jing Huang; Fupin Liu; Qunxiang Li; Su-Yuan Xie; Shangfeng Yang

So far the entrapped metals for the isolated endohedral metallofullerenes (EMFs) are primarily limited to rare earth metals, whereas except group-IVB metals, whether it is possible to entrap other d-block transition metals remains unclear. Herein we report the successful entrapment of the group-VB transition metal vanadium(V) into fullerene cage, affording the heretofore unknown V-containing EMFs. Two novel V-containing EMFs--V(x)Sc(3-x)N@C80 (x = 1, 2)--were isolated, and their molecular structures were unambiguously determined by X-ray crystallography to be I(h)(7)-C80 cage entrapping the planar VSc2N/V2ScN clusters. V(x)Sc(3-x)N@I(h)(7)-C80 (x = 1, 2) were further characterized by UV-vis-NIR and ESR spectroscopies and electrochemistry, revealing that the electronic and magnetic properties of V(x)Sc(3-x)N@I(h)(7)-C80 (x = 1, 2) are tunable upon varying the number of entrapped V atoms (i.e., x value). The molecular structures and electronic properties of V(x)Sc(3-x)N@I(h)(7)-C80 (x = 1, 2) were further compared with those of the reported analogous EMFs based on lanthanide metals and the adjacent group-IVB transition metal Ti, revealing the peculiarity of the group-VB transition metal V-based EMFs.


Journal of Materials Chemistry | 2015

Directly bonded hybrid of graphene nanoplatelets and fullerene: facile solid-state mechanochemical synthesis and application as carbon-based electrocatalyst for oxygen reduction reaction

Jian Guan; Xiang Chen; Tao Wei; Fupin Liu; Song Wang; Qing Yang; Yalin Lu; Shangfeng Yang

Using a facile solid-state mechanochemical method by ball milling, we successfully synthesized the first directly bonded graphene–C60 hybrid, for which LiOH is found to play a crucial role as the catalyst. The hybrid structure of graphene–C60 is confirmed by FTIR, Raman, XRD and XPS characterizations, and its conformation is proposed, featuring the direct bonding of graphene nanoplatelets and C60via two C–C single bonds. SEM measurement suggests that severe edge distortions occur for graphene–C60 hybrid, and HR-TEM study indicate the covalent attaching of C60 molecules onto the edge of graphene nanoplatelets. The graphene–C60 hybrid is applied as a carbon-based electrocatalyst toward oxygen reduction reaction (ORR), showing improved ORR electrocatalytic activity than the pristine graphite.


Nature Communications | 2017

Single molecule magnet with an unpaired electron trapped between two lanthanide ions inside a fullerene

Fupin Liu; Denis S. Krylov; Lukas Spree; Stanislav M. Avdoshenko; Nataliya A. Samoylova; Marco Rosenkranz; Aram Kostanyan; Thomas Greber; A. U. B. Wolter; Bernd Büchner; Alexey A. Popov

Increasing the temperature at which molecules behave as single-molecule magnets is a serious challenge in molecular magnetism. One of the ways to address this problem is to create the molecules with strongly coupled lanthanide ions. In this work, endohedral metallofullerenes Y2@C80 and Dy2@C80 are obtained in the form of air-stable benzyl monoadducts. Both feature an unpaired electron trapped between metal ions, thus forming a single-electron metal-metal bond. Giant exchange interactions between lanthanide ions and the unpaired electron result in single-molecule magnetism of Dy2@C80(CH2Ph) with a record-high 100 s blocking temperature of 18 K. All magnetic moments in Dy2@C80(CH2Ph) are parallel and couple ferromagnetically to form a single spin unit of 21 μB with a dysprosium-electron exchange constant of 32 cm−1. The barrier of the magnetization reversal of 613 K is assigned to the state in which the spin of one Dy centre is flipped.


Physical Chemistry Chemical Physics | 2002

Photoluminescence and electroluminescence of the exciplex formed between a terbium ternary complex and N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine

Hao Xin; M. Guang; Fu-You Li; Zuqiang Bian; C.H. Huang; Kurash Ibrahim; Fupin Liu

We demonstrate the photoluminescence (PL) and electroluminescence (EL) of the exciplex formed between a terbium complex tris-(1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone)-1,10-phenanthroline-terbium Tb(PMIP)3(Phen) and the hole-transporting material N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine (TPD). Experimental results show that a new emission peaking at 540 nm from their 1 : 1 mixture and the electroluminescence from the double layer device (ITO/TPD/Tb(PMIP)3(Phen)/Mg0.9Ag0.1) can be assigned to the exciplex formed between the excited state of TPD and the ground state of the terbium complex. By suppressing the formation of the exciplex by changing the carrier combination zone, pure green light from the central terbium ion with highest brightness 250 cd m−2 at 15 V, power efficiency of 0.31 lm W−1 and turn-on voltage as low as 3 V can be obtained from a device of ITO/TPD(10 nm)/Tb(PMIP)3(Phen)(80 nm)/BCP(20 nm)/Mg0.9Ag0.1. By doping TPD into the emitting layer, which facilitates the exciplex formation, bright yellow emission with highest brightness 1180 cd m−2 at 17 V was obtained from a device of ITO/TPD(20 nm)/Tb(PMIP)3(Phen) : TPD(2 : 1)(50 nm)/Tb(PMIP)3(Phen)(20 nm)/AlQ(30 nm)/Mg0.9Ag0.1.


Angewandte Chemie | 2017

Mononuclear Clusterfullerene Single-Molecule Magnet Containing Strained Fused-Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster

Fupin Liu; Song Wang; Cong-Li Gao; Qingming Deng; Xianjun Zhu; Aram Kostanyan; Rasmus Westerström; Fei Jin; Su-Yuan Xie; Alexey A. Popov; Thomas Greber; Shangfeng Yang

Abstract Fused‐pentagons results in an increase of local steric strain according to the isolated pentagon rule (IPR), and for all reported non‐IPR clusterfullerenes multiple (two or three) metals are required to stabilize the strained fused‐pentagons, making it difficult to access the single‐atom properties. Herein, we report the syntheses and isolations of novel non‐IPR mononuclear clusterfullerenes MNC@C76 (M=Tb, Y), in which one pair of strained fused‐pentagon is stabilized by a mononuclear cluster. The molecular structures of MNC@C76 (M=Tb, Y) were determined unambiguously by single‐crystal X‐ray diffraction, featuring a non‐IPR C 2v(19138)‐C76 cage entrapping a nearly linear MNC cluster, which is remarkably different from the triangular MNC cluster within the reported analogous clusterfullerenes based on IPR‐obeying C82 cages. The TbNC@C76 molecule is found to be a field‐induced single‐molecule magnet (SMM).


Fullerenes Nanotubes and Carbon Nanostructures | 2014

A Bent Tb2C2 Cluster Encaged in a CS (6)-C82 Cage: Synthesis, Isolation and X-ray Crystallographic Study

Fupin Liu; Tao Wei; Song Wang; Jian Guan; Xing Lu; Shangfeng Yang

Terbium (Tb)-based dimetallofullerene, Tb2C84, has been synthesized and isolated by multistep HPLC. According to the UV-vis-NIR spectroscopic characterization and comparison with the reported analogous M2C84 (M = Sc, Y) metallofullerenes, the molecular structure of Tb2C84 is proposed to be Tb2C2@Cs (6)-C82 featuring a metal carbide clusterfullerene (CCF) structure, which is unambiguously confirmed by X-ray crystallographic study. A detailed analysis of the crystal structure of a cocrystal of Tb2C2@Cs (6)-C82·NiII(OEP)·2C6H6 (NiII(OEP) = nickel (II) octaethylporphyrin) reveals that a bent Tb2C2 carbide cluster is encaged rigidly inside a Cs (6)-C82 cage. The C-C bond within the encaged Tb2C2 carbide cluster behaves as a typical C-C triple bond. The asymmetric unit in Tb2C2@Cs (6)-C82·NiII(OEP)·2C6H6 contains two fullerene sites, for which the encaged Tb2C2 carbide cluster however locates at nearly the same position with one Tb atom being beneath a hexagon and another Tb atom pointing to the conjunction of two adjacent hexagons.

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Shangfeng Yang

University of Pittsburgh

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Song Wang

University of Science and Technology of China

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Tao Wei

University of Science and Technology of China

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Chuanbao Chen

University of Science and Technology of China

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Mingzhi Jiao

University of Science and Technology of China

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Jian Guan

University of Science and Technology of China

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Xianjun Zhu

University of Science and Technology of China

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