Monometallic cyanide clusterfullerenes(CYCFs)with a chemical formula of MNC@C_(2)n represent a new type of clusterfullerene discovered in recent years;the encapsulated metal types are still limited to yttrium and terb...Monometallic cyanide clusterfullerenes(CYCFs)with a chemical formula of MNC@C_(2)n represent a new type of clusterfullerene discovered in recent years;the encapsulated metal types are still limited to yttrium and terbium thus far.This makes the stabilization mechanism of the host fullerene cages upon the variation of internal MNC clusters unclear.Herein,for the first time,four novel Lu-based CYCFs,namely LuNC@C_(2v)(19138)-C_(76),LuNC@C_(2)(5)-C_(82),LuNC@Cs(6)-C_(82),and LuNC@C_(2v)(9)-C_(82),have been successfully obtained and characterized using a combination of mass spectrometry,vis-NIR,single-crystal X-ray diffractometry,and cyclic voltammetry.In particular,the X-ray results of LuNC@C_(2v)(19138)-C_(76)and LuNC@C_(2)(5)-C_(82)unambiguously demonstrated that the internal LuNC unit assumes a nearly linear configuration in the small C_(76)cage but a confined triangle in the large C_(82)one,demonstrating the critical role of the cage structure in regulating the cluster configuration.Further theoretical calculations reveal that the linear and triangular configurations of LuNC clusters are governed by the strong and weak Lu-cage coordination interactions in the C_(2v)(19138)-C_(76)and C_(2)(5)-C_(82)cages,respectively.In addition,the exact positions of the internal N and C atoms inside the two cages were well defined by combining the crystallographic data with theoretical calculations,showing that the N atom always resides closer to the metal atom to pursue stronger electrostatic interactions.展开更多
Two Lu_(2)O@C_(80)isomers have been successfully isolated and unambiguously assigned as Lu_(2)O@C_(1)(31876)-C_(80)and Lu_(2)O@C_(2v)(5)-C_(80),respectively,by X-ray crystallography.Interestingly,C1(31876)-C_(80)is an...Two Lu_(2)O@C_(80)isomers have been successfully isolated and unambiguously assigned as Lu_(2)O@C_(1)(31876)-C_(80)and Lu_(2)O@C_(2v)(5)-C_(80),respectively,by X-ray crystallography.Interestingly,C1(31876)-C_(80)is an unprecedented cage with a pair of adjacent pentagons,which can be closely connected with C_(2v)(5)-C_(80)via a two-step Stone–Wales transformation.展开更多
Sodium metal is a promising anode for sodium batteries due to its high theoretical capacity and low cost.However,the serious Na dendrite growth and low Coulombic efficiency,especially at high current densities/cycling...Sodium metal is a promising anode for sodium batteries due to its high theoretical capacity and low cost.However,the serious Na dendrite growth and low Coulombic efficiency,especially at high current densities/cycling capacities,severely limit the application of sodium metal anodes.Herein,trifluoromethylfullerene,C_(60)(CF_(3))_(6),is designed as an electrolyte additive to enable the high-rate cycling of sodium metal anodes with high Coulombic efficiency.The CF3 groups contribute to the formation of stable NaF-rich solid electrolyte interface layer,while C_(60)cages induce the uniform distribution of sodium ions and promote the formation of smooth and compact morphology.Thus,Na||Cu cell with C_(60)(CF_(3))_(6)can be cycled at 2 mA·cm^(−2)and 10 mAh·cm^(−2)over 180 cycles with an average Coulombic efficiency of 99.9%,and Na||Na cell can be cycled at 10 mA·cm^(−2)over 600 cycles.Furthermore,Na||NaV2(PO_(4))_(3)@C full cell exhibits high capacity retention of 84%over 2,000 cycles at 20 C(~3 mA·cm^(−2)).展开更多
Comprehensive Summary Intramolecular interactions are fundamental for the unique structures and outstanding properties of metallofullerenes.However,how the internal metal species interplay with the cluster configurati...Comprehensive Summary Intramolecular interactions are fundamental for the unique structures and outstanding properties of metallofullerenes.However,how the internal metal species interplay with the cluster configuration inside oxide clusterfullerenes remains poorly understood.Herein,we successfully captured two oxide clusterfullerenes with different metals,namely,Lu_(2)O@C_(82)and Er_(2)O@C_(82),to elucidate the role of metal species in tuning cluster configuration.The two molecules have been fully characterized by mass spectrometry,Vis-NIR absorption spectroscopy,cyclic voltammetry,and single-crystal X-ray diffraction.展开更多
基金support from the NationalNatural Science Foundation of China(no.21925104 and 51672093)the National Postdoctoral Program for Innovative Talents(BX20190124),theChina Postdoctoral Science Foundation(2019M662584)the Natural Science Foundation of Hebei Province of China(B2019202210).
文摘Monometallic cyanide clusterfullerenes(CYCFs)with a chemical formula of MNC@C_(2)n represent a new type of clusterfullerene discovered in recent years;the encapsulated metal types are still limited to yttrium and terbium thus far.This makes the stabilization mechanism of the host fullerene cages upon the variation of internal MNC clusters unclear.Herein,for the first time,four novel Lu-based CYCFs,namely LuNC@C_(2v)(19138)-C_(76),LuNC@C_(2)(5)-C_(82),LuNC@Cs(6)-C_(82),and LuNC@C_(2v)(9)-C_(82),have been successfully obtained and characterized using a combination of mass spectrometry,vis-NIR,single-crystal X-ray diffractometry,and cyclic voltammetry.In particular,the X-ray results of LuNC@C_(2v)(19138)-C_(76)and LuNC@C_(2)(5)-C_(82)unambiguously demonstrated that the internal LuNC unit assumes a nearly linear configuration in the small C_(76)cage but a confined triangle in the large C_(82)one,demonstrating the critical role of the cage structure in regulating the cluster configuration.Further theoretical calculations reveal that the linear and triangular configurations of LuNC clusters are governed by the strong and weak Lu-cage coordination interactions in the C_(2v)(19138)-C_(76)and C_(2)(5)-C_(82)cages,respectively.In addition,the exact positions of the internal N and C atoms inside the two cages were well defined by combining the crystallographic data with theoretical calculations,showing that the N atom always resides closer to the metal atom to pursue stronger electrostatic interactions.
基金Financial support from NSFC(No.21925104,21573172,and 21773181)the Hubei Provincial Natural Science Foundation of China(No.2021CFA020)is gratefully acknowl-edged。
文摘Two Lu_(2)O@C_(80)isomers have been successfully isolated and unambiguously assigned as Lu_(2)O@C_(1)(31876)-C_(80)and Lu_(2)O@C_(2v)(5)-C_(80),respectively,by X-ray crystallography.Interestingly,C1(31876)-C_(80)is an unprecedented cage with a pair of adjacent pentagons,which can be closely connected with C_(2v)(5)-C_(80)via a two-step Stone–Wales transformation.
基金the National Science Foundation of China(Nos.21925104,51672093,51821005,U1966214,51902116,and 21975087)。
文摘Sodium metal is a promising anode for sodium batteries due to its high theoretical capacity and low cost.However,the serious Na dendrite growth and low Coulombic efficiency,especially at high current densities/cycling capacities,severely limit the application of sodium metal anodes.Herein,trifluoromethylfullerene,C_(60)(CF_(3))_(6),is designed as an electrolyte additive to enable the high-rate cycling of sodium metal anodes with high Coulombic efficiency.The CF3 groups contribute to the formation of stable NaF-rich solid electrolyte interface layer,while C_(60)cages induce the uniform distribution of sodium ions and promote the formation of smooth and compact morphology.Thus,Na||Cu cell with C_(60)(CF_(3))_(6)can be cycled at 2 mA·cm^(−2)and 10 mAh·cm^(−2)over 180 cycles with an average Coulombic efficiency of 99.9%,and Na||Na cell can be cycled at 10 mA·cm^(−2)over 600 cycles.Furthermore,Na||NaV2(PO_(4))_(3)@C full cell exhibits high capacity retention of 84%over 2,000 cycles at 20 C(~3 mA·cm^(−2)).
基金Financial support from NSFC(Nos.21925104,22171094,22201086,92261204,219010190,and 22001084)the Hubei Pro-vincial Natural Science Foundation of China(No.2021CFA020)+1 种基金the Natural Science Foundation of Jiangxi Province(No.20212BAB214029)Jiangxi“Double Thousand Plan”is grate-fully acknowledged.We thank the staff in BL17B beamline of National Center for Protein Sciences Shanghai(NCPSS)at Shanghai Synchrotron Radiation Facility for the assistance with data collection.
文摘Comprehensive Summary Intramolecular interactions are fundamental for the unique structures and outstanding properties of metallofullerenes.However,how the internal metal species interplay with the cluster configuration inside oxide clusterfullerenes remains poorly understood.Herein,we successfully captured two oxide clusterfullerenes with different metals,namely,Lu_(2)O@C_(82)and Er_(2)O@C_(82),to elucidate the role of metal species in tuning cluster configuration.The two molecules have been fully characterized by mass spectrometry,Vis-NIR absorption spectroscopy,cyclic voltammetry,and single-crystal X-ray diffraction.
