Citation: ZHAO Lei, WAN Shi-Gang, CHEN Cheng-Dong, LIN Yi-ji, FANG Xue-Ming, ZHANG Hui. Mirror Symmetry Breaking and Absolute Configuration Correlations of Fe(III) Complexes with Achiral Substituted o-Iminobenzosemiquinonato Ligands[J]. Acta Physico-Chimica Sinica, ;2013, 29(06): 1183-1191. doi: 10.3866/PKU.WHXB201304122
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A pair of chiral o-iminobenzosemiquinonato Fe(III) complexes, Λ-mer- [Fe(LISQ)3] and Δ-mer-[Fe(LISQ)3] (LISQ: 2-phenylimino-4, 6-di-tert-butylphenol, mer: meridian configuration), were synthesized from 2-anilino-4,6-di-tert-butylphenol (H2L) and FeCl2·4H2O. 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-atmetal o-iminobenzosemiquinonato M(III) complexes [M(LISQ)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%.
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