Endohedral clusterfullerenes featuring the encapsulation of metal clusters within carbon cages exhibit intriguing physical and chemical properties inaccessible to empty fullerenes.Thus far,their syntheses are predomin...Endohedral clusterfullerenes featuring the encapsulation of metal clusters within carbon cages exhibit intriguing physical and chemical properties inaccessible to empty fullerenes.Thus far,their syntheses are predominantly fulfilled by using gaseous sources,suffering from low yield,and requiring an additional gas inlet and a heating pretreatment up to 1000℃.Herein,we employ an ancient pigment,Prussian blue(Fe_(4)[Fe(CN)_(6)]_(3)),as a cheap solid cyanide/nitrogen dual-source,affording the simplified yet high-yield simultaneous syntheses of novel dysprosium(D_(y))-based metal cyanide clusterfullerenes(CYCFs)D_(y)CN@C_(2n)and metal nitride clusterfullerenes D_(y3)N@C_(2n).Surprisingly,the(CN)−anion of Fe_(4)[Fe(CN)_(6)]_(3)survives under the extremely high temperature(up to 4000 K)of plasma generated via DC-arc discharge,and functions as the cyanide source of CYCFs.Under the optimized D_(y):[CN]:C molar ratio of 1:1:15,the sum yield of isolated D_(y)CN@C_(2n)(2n=76,82)CYCFs produced using Fe_(4)[Fe(CN)_(6)]_(3)is about 2.8 times higher than that obtained using gaseous N_(2)source.Moreover,the molecular structures of the three isomers of D_(y)CN@C_(82)are unambiguously determined by single-crystal X-ray diffraction,indicating that the encapsulated triangular D_(y)CN cluster is tunable due to strong metal–cage interactions.This study paves the way for the low-cost and high-yield syntheses of pricey endohedral fullerenes.展开更多
基金partially supported by the National Key Research and Development Program of China(2017YFA0402800)the National Natural Science Foundation of China(51925206,U1932214,21721001 and 91961113)。
文摘Endohedral clusterfullerenes featuring the encapsulation of metal clusters within carbon cages exhibit intriguing physical and chemical properties inaccessible to empty fullerenes.Thus far,their syntheses are predominantly fulfilled by using gaseous sources,suffering from low yield,and requiring an additional gas inlet and a heating pretreatment up to 1000℃.Herein,we employ an ancient pigment,Prussian blue(Fe_(4)[Fe(CN)_(6)]_(3)),as a cheap solid cyanide/nitrogen dual-source,affording the simplified yet high-yield simultaneous syntheses of novel dysprosium(D_(y))-based metal cyanide clusterfullerenes(CYCFs)D_(y)CN@C_(2n)and metal nitride clusterfullerenes D_(y3)N@C_(2n).Surprisingly,the(CN)−anion of Fe_(4)[Fe(CN)_(6)]_(3)survives under the extremely high temperature(up to 4000 K)of plasma generated via DC-arc discharge,and functions as the cyanide source of CYCFs.Under the optimized D_(y):[CN]:C molar ratio of 1:1:15,the sum yield of isolated D_(y)CN@C_(2n)(2n=76,82)CYCFs produced using Fe_(4)[Fe(CN)_(6)]_(3)is about 2.8 times higher than that obtained using gaseous N_(2)source.Moreover,the molecular structures of the three isomers of D_(y)CN@C_(82)are unambiguously determined by single-crystal X-ray diffraction,indicating that the encapsulated triangular D_(y)CN cluster is tunable due to strong metal–cage interactions.This study paves the way for the low-cost and high-yield syntheses of pricey endohedral fullerenes.
