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CO2 fixation by macrocyclic nickel(II) complexes: synthesis and structures of helical chains constructed via hydrogen bonds involving imidazole

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Abstract

Two dinuclear carbonato-bridged nickel(II) complexes formulated as [Ni(rac-L)]2(µ-CO3)(H2O)(im)4(ClO4)2 (1) and [Ni(SS-L)]2(µ-CO3)(H2O)(im)4(ClO4)2 (2) (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, im = imidazole) were isolated from the reactions of [Ni(rac-L)](ClO4)2 and [Ni(SS-L)](ClO4)2 with imidazole in the air, respectively, and a hydrocarbonato-coordinated nickel(II) complex formulated as [Ni(rac-L)](HCO3)(ClO4) (3) was reacted with obtained when [Ni(rac-L)](ClO4)2 reacted with l-cysteine under weakly basic conditions in the air. We found that the macrocyclic nickel(II) complexes can easily take up and fix atmospheric CO2 at room temperature. Single-crystal X-ray diffraction analyses revealed of all three complexes that the central Ni(II) atoms all have a six-coordinated distorted octahedral coordination geometry, and the carbonate anion bridges two Ni(II) atoms in a tridentate fashion to form dimers in complexes 1 and 2, and the hydrocarbonate coordinates with Ni(II) in a didentate fashion in complex 3. The monomers of {[Ni(RR-L)]2(µ-CO3)(H2O)}2+/{[Ni(SS-L)]2(µ-CO3)(H2O)}2+ are connected through hydrogen bonds to generate one-dimensional right- and left-handed helical chains in complex 1. The chiral nature of complex 2 has been confirmed by CD spectroscopy.

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Acknowledgments

This work was supported by the Natural Science Foundation of Hunan Province (2015JJ2072), the Construct Program of the Key Discipline in Hunan Province (2011-76), the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province (2012-318), the Program for Excellent Talents in Hunan University of Science and Engineering (2013).

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Authors and Affiliations

  1. Department of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou, 425199, Hunan, China

    Guang-Chuan Ou, Fang Liu, Man-Hua Ding & Xian-You Yuan

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  1. Guang-Chuan Ou
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  2. Fang Liu
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  3. Man-Hua Ding
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  4. Xian-You Yuan
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Correspondence to Guang-Chuan Ou.

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Ou, GC., Liu, F., Ding, MH. et al. CO2 fixation by macrocyclic nickel(II) complexes: synthesis and structures of helical chains constructed via hydrogen bonds involving imidazole. Transition Met Chem 40, 171–178 (2015). https://doi.org/10.1007/s11243-014-9903-0

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