Control of coordination and luminescence properties of lanthanide complexes using octadentate oligopyridine-amine ligands

八座オリゴピリジンアミン配位子を用いた希土類錯体の構造制御と発光特性制御

和田 淳*; 渡邉 雅之   ; 山野井 慶徳*; 南川 卓也 ; 並木 康祐*; 山崎 幹夫*; 村田 昌樹*; 西原 寛*

Wada, Atsushi*; Watanabe, Masayuki; Yamanoi, Yoshinori*; Nankawa, Takuya; Namiki, Kosuke*; Yamasaki, Mikio*; Murata, Masaki*; Nishihara, Hiroshi*

直鎖状及び環状の骨格を有するオリゴピリジン配位子の希土類錯体を合成し、その構造をX線結晶構造解析により明らかにした。錯体はすべて歪んだCapped Square Antiprism (CSAP)構造をとり、直鎖状骨格を持つ配位子のほうがより歪んだ構造を取ることを明らかにした。また、Eu錯体では、直鎖状の歪んだ構造を持つ錯体の方が、より強い発光を示すことを世界に先駆けて見いだした。これらの結果は、多座配位子の幾何構造を制御することで、発光特性を制御できることを示している。

Lanthanide complexes with linear and cyclic octadentate oligopyridine-amine ligands were synthesized, and their molecular structures were determined by single-crystal X-ray crystallography. All of the complexes had a distorted capped square antiprism (CSAP) geometry, and the coordination environments of lanthanide complexes were more distortedfor the complexes with the linear ligand than those with the cyclic ligand. The Eu complexes with the linear ligand showed more intense emissions, which were attributed to the D F transition, than the complex withthe cyclic ligand in acetonitrile, which can be attributed to the distortion in the coordination environments. These results indicate that the coordination environments of lanthanide complexes, and thus the luminescence properties, can be controlled by tuning the geometrical structures of polydentate ligands.