化学
三斜晶系
非对映体
对映体
结晶学
绝对构型
手性(物理)
酞菁
圆二色性
立体化学
晶体结构
有机化学
物理
量子力学
手征对称破缺
Nambu–Jona Lasinio模型
夸克
作者
Yang Zhou,Yuexing Zhang,Hailong Wang,Jianzhuang Jiang,Yongzhong Bian,Atsuya Muranaka,Nagao Kobayashi
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2009-08-18
卷期号:48 (18): 8925-8933
被引量:32
摘要
Mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes [HM(III){Pc(alpha-3-OC(5)H(11))(4)}{TOAPP}] [Pc(alpha-3-OC(5)H(11))(4) = 1,8,15,22-tetrakis(3-pentyloxy)-phthalocyaninate; TOAPP = meso-tetrakis(4-octylamino-phenyl)porphyrinate; M = Y (1), Ho (2)] were prepared as a racemic mixture by treating metal-free phthalocyanine H(2)Pc(alpha-3-OC(5)H(11))(4) with half-sandwich complexes [M(III)(acac)(TOAPP)], generated in situ from M(acac)(3).nH(2)O and H(2)TAPP [TAPP = meso-tetrakis(4-amino-phenyl)porphyrinate], in refluxing 1-octanol. The obtained double-deckers were characterized by elemental analysis and various spectroscopic methods. The molecular structures of 1 and 2 were determined by single-crystal X-ray diffraction analysis. The compounds crystallize in the triclinic system with a pair of enantiomeric double-deckers per unit cell. Resolution of 1 and 2 was achieved using a chiral HPLC technique combined with the formation of their diastereomeric mixture using L-Boc-Phe-OH as the chiral resolving agent, yielding for the first time the pure diastereoisomers of chiral mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes with C(4) symmetry. The absolute configuration of these chiral complexes was assigned by comparing the experimental circular dichroism spectrum with a simulated one on the basis of time-dependent density functional theory calculations.
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