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

来源 :Science in China(Series B:Chemistry) | 被引量 : 0次 | 上传用户:yizhonglishi
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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. Eight-coordinate chiral lanthanide complexes [Eu (dbm) 3LRR] (1) [Eu (dbm) 3LSS] and [Tb (dbm) 3LRR] (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. 2 were obtained by combination of the solid-state CD spectra and the crystal structure analysis. Yet further with the solid-state CD spectra of six-coordinate and seven-coordinate metal complexes containing β-diketone ligands, the CD spectra absolute 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 .
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