手性八配位镧系络合物的立体化学与固体CD光谱  

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

作　　者：周南[1] 万仕刚[1] 赵健[1] 林以玑[1] 宣为民[1] 方雪明[1] 章慧[1] 

机构地区：[1]固体表面物理化学国家重点实验室、厦门大学化学化工学院化学系,厦门361005

出　　处：《中国科学（B辑）》2009年第11期1395-1401,共7页Science in China(Series B)

基　　金：国家自然科学基金(批准号:20773098,20973136);厦门大学科技创新工程基金(系列2)(批准号:XDKJCX20061027)资助

摘　　要：本文立体选择性地合成了八配位Ln(Ⅲ)络合物[Eu(dbm)3LRR](1)、[Eu(dbm)3LSS](2)和[Tb(dbm)3LRR](3)(LRR/LSS=(-)/(+)-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Δ或Λ绝对构型也被其单晶结构所证实.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.

关 键 词：八配位镧系络合物 Β-二酮 手性联吡啶 晶体结构 固体CD光谱 绝对构型 

分 类 号：O641.6[理学—物理化学]