Eight-coordinate chiral lanthanide complexes [Eu(dbm)3LRR](1),[Eu(dbm)3LSS](2) and [Tb(dbm)3LRR](3)(LRR/LSS =(-)-/(+)-4,5-pineno-2,2'-bipyridine,Hdbm = dibenzoylmethane) were synthesized stereoselectively,which we...Eight-coordinate chiral lanthanide complexes [Eu(dbm)3LRR](1),[Eu(dbm)3LSS](2) and [Tb(dbm)3LRR](3)(LRR/LSS =(-)-/(+)-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 mirrorimage structure features of 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 of six-coordinate and seven-coordinate metal complexes containing β-diketone ligands,the CD spectraabsolute configuration correlation rule for the eight-coordinate β-diketonate lanthanide complexes was proposed through the exciton chirality method for the first time.The △ or Λ absolute configurations of complexes 1―3 with the distorted square antiprism geometry were confirmed by the X-ray single-crystal analysis.展开更多
基金Supported by the National Natural Science Foundation of China (Grant Nos. 20773098 & 20973136)the Innovation Foundation of Xiamen University (Series 2) (Grant No. XDKJCX20061027)
文摘Eight-coordinate chiral lanthanide complexes [Eu(dbm)3LRR](1),[Eu(dbm)3LSS](2) and [Tb(dbm)3LRR](3)(LRR/LSS =(-)-/(+)-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 mirrorimage structure features of 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 of six-coordinate and seven-coordinate metal complexes containing β-diketone ligands,the CD spectraabsolute configuration correlation rule for the eight-coordinate β-diketonate lanthanide complexes was proposed through the exciton chirality method for the first time.The △ or Λ absolute configurations of complexes 1―3 with the distorted square antiprism geometry were confirmed by the X-ray single-crystal analysis.
