手性八配位镧系络合物的立体化学与固体CD光谱

本文立体选择性地合成了八配位Ln（III）络合物Eu（dbm）3L^RR]（1）、Eu（dbm）3L^SS]（2）和Tb（dbm）3L^RR]（3）（L^RR／L^SS=（-）／（＋）-4，5-蒎烯基联吡啶，Hdbm=二苯甲酰甲烷），利用单晶衍射、Uv-vis和固体CD光谱对其进行了表征．晶体结构分析和固体CD光谱表明1和2互为对映体．采用激子手性方法，通过与六配位和七配位的β-二酮络合物的固体CD光谱的对比，提出含β-二酮的八配位Ln（III）络合物的绝对构型关联规则．该系列络合物的畸变四方反棱柱的△或∧绝对构型也被其单晶结构所证实．

Stereochemistry and solid-state circular dichroism spectroscopy of eight-coordinate chiral lanthanide complexes

Eight-coordinate chiral lanthanide complexes Eu（dbm）3L^RR]（1）, Eu（dbm）3L^SS]（2） and Tb（dbm）3L^RR]（3） （L^RR/L^SS = （-）/（＋）-4,5-pineno-2,2＇-bipyridine, Hdbm = dibenzoylmethane） were synthesized stereoselectively, which were characterized by UV-vis, CD spectra and X-ray single-crystal diffraction. The mirror-image structure features of the complexes 1 and 2 were obtained by combination of the solid-state CD spectra and the crystal structure analysis. After further comparison with the solid-state CD spectra containing β-diketone ligands, the CD spectra-absolute of six-coordinate and seven-coordinate metal complexes configuration correlation rule for the eight-coordinate β-diketonate lanthanide complexes was proposed through the exciton chirality method for the first time. The A or A absolute configurations of the complexes 1-3 with the distorted square antiprism geometry were confirmed by X-ray single-crystal analysis.