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具有左手/右手螺旋性的一维螺旋链的构建:一维链的螺旋性与构建单元手性之间的相关性。

Constructions of 1D helical chains with left-handed/right-handed helicity: a correlation between the helicity of 1D chains and the chirality of building blocks.

作者信息

Zheng Xiao-Dan, Jiang Long, Feng Xiao-Long, Lu Tong-Bu

机构信息

MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, and School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, China.

出版信息

Dalton Trans. 2009 Sep 14(34):6802-8. doi: 10.1039/b904081a. Epub 2009 Jul 7.

Abstract

The reactions of Ni(alpha-SS-L)(2)/Ni(alpha-RR-L)(2) with dca(-) gave two enantiomers of Ni(SS-L)(2) (S-) and Ni(RR-L)(2) (R-) in acetonitrile/water, and two supramolecular stereoisomers of {Ni(SS-L)(dca)(3)(ClO(4)).DMF}(n) (Delta-) and {Ni(RR-L)(dca)(3)(ClO(4)).DMF}(n) (Lambda-) in acetonitrile/DMF, respectively (L = 5,5,7,12,12, 14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, dca = dicyanamide, N(CN)(2)(-)). While the reaction of racemic Ni(alpha-rac-L)(2) (containing an equal amount of SS and RR enantiomers) with dca(-) in acetonitrile/water or acetonitrile/DMF produced a trimer of Ni(rac-L)(dca).(dca).(ClO(4))(2).MeCN () rather than S-/R- or Delta-/Lambda-. X-ray single-crystal analysis reveals that S-/R- and Delta-/Lambda- crystallize in a chiral space group P2(1), while crystallizes in a centrosymmetric space group C2/c. In S-/R-, the Ni(SS-L)(2)/Ni(RR-L)(2) monomers are linked through intermolecular hydrogen bonds to form a two-dimensional sheet. While the intermolecular hydrogen bonding linking of {Ni(SS-L)(dca)(3)}(+)/{Ni(RR-L)(dca)(3)}(+) leads to the formation of a 1D right-handed helical chain of Delta- and 1D left-handed helical chain of Lambda-, respectively, demonstrating there is a correlation between the helicity of 1D chains and the chirality of building blocks. Complex forms a triangular structure of {Ni(rac-L)(dca)}(3+), in which the macrocyclic ligand L adopts unsymmetrical RR/RR/SS or RR/SS/SS configurations. The homochiral nature of S-/R- and Delta-/Lambda- are confirmed by the results of solid circular dichroism (CD) spectra measurements. The magnetic properties of chiral Delta-/Lambda- and achiral were investigated.

摘要

Ni(α-SS-L)₂/Ni(α-RR-L)₂与dca⁻在乙腈/水中反应生成了Ni(SS-L)₂的两种对映体(S-)和Ni(RR-L)₂(R-),而在乙腈/DMF中反应分别生成了{[Ni(SS-L)]₂(dca)₃(ClO₄).DMF}ₙ(Δ-)和{[Ni(RR-L)]₂(dca)₃(ClO₄).DMF}ₙ(Λ-)的两种超分子立体异构体(L = 5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷,dca = 二氰胺,N(CN)₂⁻)。而外消旋的Ni(α-rac-L)₂(含有等量的SS和RR对映体)与dca⁻在乙腈/水或乙腈/DMF中反应生成了[Ni(rac-L)(dca)]₃.(dca).(ClO₄)₂.MeCN ( )的三聚体,而非S-/R-或Δ-/Λ-。X射线单晶分析表明,S-/R-和Δ-/Λ-结晶于手性空间群P2₁,而 结晶于中心对称空间群C2/c。在S-/R-中,Ni(SS-L)₂/Ni(RR-L)₂单体通过分子间氢键相连形成二维片层结构。而{[Ni(SS-L)]₂(dca)₃}(+)/{[Ni(RR-L)]₂(dca)₃}(+)之间的分子间氢键连接分别导致形成了Δ-的一维右手螺旋链和Λ-的一维左手螺旋链,表明一维链的螺旋度与结构单元的手性之间存在关联。配合物形成了{[Ni(rac-L)(dca)]₃}³⁺的三角结构,其中大环配体L采用不对称的RR/RR/SS或RR/SS/SS构型。通过固体圆二色性(CD)光谱测量结果证实了S-/R-和Δ-/Λ-的同手性性质。对手性Δ-/Λ-和非手性 的磁性进行了研究。

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