新型双（水杨醛缩氨）四氧肟酸配体构筑的异核三核 Co(II)-Ce(III) 配合物的合成及荧光性质

Synthesis and Fluorescence Properties of a New Heterotrinuclear Co(II)-Ce(III)Complex Constructed from a bis(salamo)-Type Tetraoxime Ligand.

机构信息

College of Science, Gansu Agricultural University, Lanzhou 730070, China.

School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China.

出版信息

Molecules. 2018 Mar 31;23(4):804. doi: 10.3390/molecules23040804.

[Co₂(L)Ce(OAc)₃(CH₃CH₂OH)]·1.5CH₃OH∙0.5CH₂Cl₂, a heterotrinuclear Co(II)-Ce(III) bis(salamo)-type complex with a symmetric bi(salamo)-type ligand H₄L and an acyclic naphthalenediol moiety, was designed, synthesized and characterized by elemental analyses, FT-IR, UV-Vis and fluorescence spectroscopy and X-ray crystallography. The X-ray crystallographic investigation revealed the heterotrinuclear complex consisted of two Co(II) atoms, one Ce(III) atom, one (L) unit, three ₂-acetate ions, one coordinated ethanol molecule, one and half crystallization methanol molecule and half crystallization dichloromethane molecule. Two Co(II) atoms located in the N₂O₂ coordination spheres, are both hexacoordinated, with slightly distorted octahedral geometries. The Ce(III) atom is nine-coordinated and located in the O₆ cavity possesses a single square antiprismatic geometry. In addition, supramolecular interactions exist in the Co(II)-Ce(III) complex. Two infinite 2D supramolecular structures are built via intermolecular O-H···O, C-H···O and C-H··· interactions, respectively.

[Co₂(L)Ce(OAc)₃(CH₃CH₂OH)]·1.5CH₃OH∙0.5CH₂Cl₂，一种具有对称双（水杨醛亚胺）配体 H₄L 和非循环萘二酚部分的异核双核 Co(II)-Ce(III) 双水杨醛亚胺型配合物，通过元素分析、FT-IR、UV-Vis 和荧光光谱以及 X 射线晶体学进行了设计、合成和表征。X 射线晶体学研究表明，该异核多核配合物由两个 Co(II)原子、一个 Ce(III)原子、一个 (L)单元、三个 ₂-乙酸根离子、一个配位的乙醇分子、一个半结晶甲醇分子和半个结晶二氯甲烷分子组成。两个 Co(II)原子位于 N₂O₂配位球中，均为六配位，具有略微扭曲的八面体几何形状。Ce(III)原子为九配位，位于 O₆腔中，具有单一的正方形反棱柱几何形状。此外，在 Co(II)-Ce(III)配合物中存在超分子相互作用。通过分子间 O-H···O、C-H···O 和 C-H···π 相互作用，分别构建了两个无限的 2D 超分子结构。