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dc.contributor.author赵檑
dc.contributor.author万仕刚
dc.contributor.author陈成栋
dc.contributor.author林以玑
dc.contributor.author方雪明
dc.contributor.author章慧
dc.date.accessioned2016-05-17T02:53:17Z
dc.date.available2016-05-17T02:53:17Z
dc.date.issued2013-06-15
dc.identifier.citation物理化学学报,2013,29:73-81
dc.identifier.issn1000-6818
dc.identifier.otherWLHX201306010
dc.identifier.urihttps://dspace.xmu.edu.cn/handle/2288/106820
dc.description.abstract以2-苯胺基-4,6-二叔丁基苯酚(H2l) 和 fECl2·4H2O 为原料制备了一对手性半醌 fE(III) 络合物Λ-MEr-[fE(lISQ)3]和Δ-MEr-[fE(lISQ)3] (lISQ: 2-苯亚胺基-4,6-二叔丁基苯酚, MEr : 经式构型), 通过单晶 X 射线衍射分析结合单晶压制片膜的固体圆二色(Cd)光谱确定了该络合物的绝对构型, 在此基础上建立了此类半醌络合物[M(lISQ)3] (M=Cr, fE, CO)的惟手性金属中心绝对构型与固体 Cd 光谱之间的关联. 此外, 还对 10 份合成的[fE(lISQ)3]的大宗产物粉末与单晶的固体 Cd 谱进行了比对分析, 以及对 1 份合成产物进行 10 次重结晶的固体Cd 光谱表征. 研究表明该化合物在结晶过程中发生了镜面对称性破缺 (MSb), 对映体过量 (EE) 值在15%-100%之间.
dc.description.abstractA pair of chiral o-iminobenzosemiquinonato Fe(Ⅲ) complexes, Λ-mer-[Fe(L ISQ ) 3 ] and Δ-mer- [Fe(L ISQ ) 3 ] (L ISQ : 2-phenylimino-4,6-di-tert-butylphenol, mer : meridian configuration), were synthesized from 2-anilino-4,6-di-tert-butylphenol (H 2 L) and FeCl 2 · 4H 2 O.Their absolute configurations were determined by single crystal X-ray diffraction (XRD) and solid-state circular dichroism (CD) spectra (the same single crystal for XRD was dispersed in KCl).Correlations between the absolute configurations of the chiral-at- metal o-iminobenzosemiquinonato M(Ⅲ) complexes [M(L ISQ ) 3 ] (M=Cr, Fe, Co) and their solid-state CD spectra were also established.Comparison between solid-state CD spectra of the bulk samples from 10 different syntheses and their single crystals were thoroughly analyzed.The solid-state CD spectra of the powdered samples from 10 different crystallizations of one product were characterized.These studies indicated that mirror symmetry breaking (MSB) occurred during the crystallization process of the Fe(Ⅲ) complexes and their enantiomeric excess (ee) values were between 15% and 100%.
dc.description.sponsorship国家自然科学基金(21273175;20973136)资助项目~~
dc.language.isozh_CN
dc.subject半醌Fe(Ⅲ)络合物
dc.subject镜面对称性破缺
dc.subject绝对构型
dc.subject固体CD光谱
dc.subject单晶X射线衍射
dc.subjectSemiquinone Fe(Ⅲ) complexes
dc.subjectMirror symmetry breaking
dc.subjectAbsolute configuration
dc.subjectSolid-state CD spectroscopy
dc.subjectSingle crystal X-ray diffraction
dc.title基于非手性邻苯酚胺衍生物的半醌Fe(Ⅲ)络合物的镜面对称性破缺及其绝对构型关联
dc.title.alternativeMirror Symmetry Breaking and Absolute Configuration Correlations of Fe(Ⅲ) Complexes with Achiral Substituted o-Iminobenzosemiquinonato Ligands
dc.typeArticle


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