• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >The Unanticipated Dimerization of Ce@C-2v(9)-C-82 upon Co-crystallization with Ni(octaethylporphyrin) and Comparison with Monomeric M@C-2v(9)-C-82 (M = La, Sc, and Y)
【24h】

The Unanticipated Dimerization of Ce@C-2v(9)-C-82 upon Co-crystallization with Ni(octaethylporphyrin) and Comparison with Monomeric M@C-2v(9)-C-82 (M = La, Sc, and Y)

机译：与镍（八乙基卟啉）共结晶时Ce @ C-2v（9）-C-82的意外二聚和与单体M @ C-2v（9）-C-82的比较（M = La，Sc和Y ）

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

We report that Ce@C-2v(9)-C-82 forms a centrosymmetric dimer when co-crystallized with Ni(OEP) (OEP = octaethylporphyrin dianion). The crystal structure of {Ce@C-2v(9)-C-82}(2)center dot 2[Ni(OEP)]center dot 4C(6)H(6) shows that a new C-C bond with a bond length of 1.605(5) angstrom connects the two cages. The high spin density of the singly occupied molecular orbital (SOMO) on the cage and the pyramidalization of the cage are factors that favor dimerization. In contrast, the treatment of Ni(OEP) with M@C-2v(9)-C-82 (M = La, Sc, and Y) results in crystallization of monomeric endohedral fullerenes. A systematic comparison of the X-ray structures of M@C-2v(9)-C-82 (M = Sc, Y, La, Ce, Gd, Yb, and Sm) reveals that the major metal site in each case is located at an off-center position adjacent to a hexagonal ring along the C-2 axis of the C-2v(9)-C-82 cage. DFT calculations at the M06-2X level revealed that the positions of the metal centers in these metallofullerenes M@C-2v(9)-C-82 (M = Sc, Y, and Ce), as determined by single-crystal X-ray structure studies, correspond to an energy minimum for each compound.
机译：我们报告说Ce @ C-2v（9）-C-82与Ni（OEP）（OEP =八乙基卟啉二价阴离子）共结晶时会形成一个中心对称的二聚体。 {Ce @ C-2v（9）-C-82}（2）中心点2 [Ni（OEP）]中心点4C（6）H（6）的晶体结构表明具有键长的新CC键1.605（5）埃的距离将两个笼子连接起来。笼子上单个占据的分子轨道（SOMO）的高自旋密度和笼子的锥体化是有利于二聚化的因素。相反，用M @ C-2v（9）-C-82（M = La，Sc和Y）处理Ni（OEP）会导致单体内膜富勒烯结晶。系统地比较M @ C-2v（9）-C-82的X射线结构（M = Sc，Y，La，Ce，Gd，Yb和Sm）表明，每种情况下的主要金属位点是位于沿着C-2v（9）-C-82笼的C-2轴与六角环相邻的偏心位置。 D06在M06-2X级的计算表明，在这些金属富勒烯M @ C-2v（9）-C-82（M = Sc，Y和Ce）中，金属中心的位置由单晶X-射线结构研究，对应于每种化合物的最低能量。

著录项

相似文献

  • 外文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号