Acta Phys. -Chim. Sin. ›› 2013, Vol. 29 ›› Issue (06): 1183-1191.doi: 10.3866/PKU.WHXB201304122


Mirror Symmetry Breaking and Absolute Configuration Correlations of Fe(III) Complexes with Achiral Substituted o-Iminobenzosemiquinonato Ligands

ZHAO Lei, WAN Shi-Gang, CHEN Cheng-Dong, LIN Yi-Ji, FANG Xue-Ming, ZHANG Hui   

  1. State Key Laboratory of Physical Chemistry of Solid Surface, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
  • Received:2013-01-25 Revised:2013-04-09 Published:2013-05-17
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21273175, 20973136).


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%.

Key words: Semiquinone Fe(III) complexes, Mirror symmetry breaking, Absolute configuration, Solid-state CD spectroscopy, Single crystal X-ray diffraction