Citation: LIU Cheng-Yong, YAN Jian-Xin, LIN Yi-Ji, LI Dan, FANG Xue-Ming, ZHANG Hui. Mirror Symmetry Breaking of cis-[Ni(NCS)₂tren]: Special Chiral Conformations of Chelate Rings[J]. Acta Physico-Chimica Sinica, ;2012, 28(02): 257-264. doi: 10.3866/PKU.WHXB201112091 shu

Mirror Symmetry Breaking of cis-[Ni(NCS)₂tren]: Special Chiral Conformations of Chelate Rings

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 Date: 28 September 2011
Available Online: 9 December 2011
Fund Project: 国家自然科学基金(20773098, 20973136)资助项目 (20773098, 20973136)

In order to explore the chiral origin of cis-[Ni(NCS)₂tren] [tren: tris(2-aminoethyl) amine], a pair of chiral crystals of cis-[Ni(NCS)₂tren] was characterized by X-ray single crystal structural analysis, solution UV-Vis-near infrared (NIR) spectroscopy, solid state UV-circular dichiroism (CD), and powder X-ray diffraction (XRD) spectra. The results indicated that the chiral crystals of cis-[Ni(NCS)₂tren] were obtained by mirror symmetry-breaking crystallization, and the special chiral ring conformations (δδλ, λλδ) of the coordinated tripod-type tren ligands are responsible for the chiral origin of cis-[Ni(NCS)₂tren]. The Cotton effects of Ni(II) complexes in the solid-state UV-CD spectra are presumably attributed to the π-π^* and charge-transfer chromophores of the NCS^- ligands by the chiral perturbation of the helical ring conformations and metal-centered chirality. According to the statistical results of solid-state CD spectra of cis-[Ni(NCS)₂tren] for twenty batch syntheses, their enantiomeric excess (ee) values are between 39% and 100%.
- Chirality,
- Mirror symmetry breaking,
- Ring conformational isomerism,
- Tris(2-aminoethyl)amine,
- Solid state CD spectroscopy
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Mirror Symmetry Breaking of cis-[Ni(NCS)2tren]: Special Chiral Conformations of Chelate Rings

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Mirror Symmetry Breaking of cis-[Ni(NCS)₂tren]: Special Chiral Conformations of Chelate Rings