title: Sc2O@C(2v)(5)-C80: Dimetallic Oxide Cluster Inside a C80 Fullerene Cage.
abstract: A new oxide cluster fullerene, Sc2O@C(2v)(5)-C80, has been isolated and characterized by mass spectrometry, UV-vis-NIR absorption spectroscopy, cyclic voltammetry, (45)Sc NMR, DFT calculations, and single crystal X-ray diffraction. The crystallographic analysis unambiguously elucidated that the cage symmetry was assigned to C(2v)(5)-C80 and suggests that the Sc2O cluster is ordered inside the cage. The crystallographic data further reveals that the Sc1-O-Sc2 angle is much larger than that found in Sc2O@T(d)(19151)-C76 but almost comparable to that in Sc2O@Cs(6)-C82, suggesting that the endohedral Sc2O unit is flexible and can display large variation in the Sc-O-Sc angle, which depends on the size and shape of the cage. Computational studies show that there is a formal transfer of four electrons from the Sc2O unit to the C80 cage, i.e., (Sc2O)(4+)@(C80)(4-), and the HOMO and LUMO are mainly localized on the C80 framework. Moreover, thermal and entropic effects are seen to be relevant in the isomer selection. Comparative studies between the recently reported Sc2C2@C(2v)(5)-C80 and Sc2O@C(2v)(5)-C80 reveal that, despite their close structural resemblance, subtle differences exist on the crystal structures, and the clusters exert notable impact on their spectroscopic properties as well as interactions between the clusters and corresponding cages.
authors.affiliation: Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, China.
authors.forename: Qiangqiang
authors.initials: Q
authors.lastname: Tang
authors.affiliation: Departament de Química Física i Inorgànica, Universitat Rovira i Virgili , c/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
authors.forename: Laura
authors.initials: L
authors.lastname: Abella
authors.affiliation: College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University , Suzhou 215006, China.
authors.forename: Yajuan
authors.initials: Y
authors.lastname: Hao
authors.affiliation: Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, China.
authors.forename: Xiaohong
authors.initials: X
authors.lastname: Li
authors.affiliation: Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, China.
authors.forename: Yingbo
authors.initials: Y
authors.lastname: Wan
authors.affiliation: Departament de Química Física i Inorgànica, Universitat Rovira i Virgili , c/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
authors.forename: Antonio
authors.initials: A
authors.lastname: Rodríguez-Fortea
authors.affiliation: Departament de Química Física i Inorgànica, Universitat Rovira i Virgili , c/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
authors.forename: Josep M
authors.initials: JM
authors.lastname: Poblet
authors.affiliation: College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University , Suzhou 215006, China.
authors.forename: Lai
authors.initials: L
authors.lastname: Feng
authors.affiliation: Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, China.
authors.forename: Ning
authors.initials: N
authors.lastname: Chen