• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

三钴扩展金属原子链的对映体拆分与X射线光学活性

Enantiomeric resolution and X-ray optical activity of a tricobalt extended metal atom chain.

作者信息

Srinivasan Anandi, Cortijo Miguel, Bulicanu Vladimir, Naim Ahmad, Clérac Rodolphe, Sainctavit Philippe, Rogalev Andrei, Wilhelm Fabrice, Rosa Patrick, Hillard Elizabeth A

机构信息

CNRS , CRPP , UPR 8641 , F-33600 Pessac , France . Email:

Univ. Bordeaux , CRPP , UPR 8641 , F-33600 Pessac , France.

出版信息

Chem Sci. 2017 Dec 4;9(5):1136-1143. doi: 10.1039/c7sc04131d. eCollection 2018 Feb 7.

DOI:10.1039/c7sc04131d
PMID:29675158
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5884025/
Abstract

A simple procedure based on anion exchange was employed for the enantiomeric resolution of the extended metal atom chain (EMAC) [Co(dpa)(MeCN)]. Use of the chiral salt (NBu)[As(tartrate)], (Λ- or Δ-), resulted in the selective crystallization of the EMAC enantiomers as Δ-Co(dpa)(MeCN)[Λ-As(tartarte)], (Δ-) and Λ-Co(dpa)(MeCN)[Δ-As(tartrate)] (Λ-), respectively, in the 422 space group, whereas a racemic mixture of yielded [Co(dpa)(MeCN)][As(tartrate)]·2MeCN (-), which crystallized in the 2/ space group. The local electronic and magnetic structure of the EMAC enantiomers was studied, exploiting a variety of dichroisms in single crystals. A strong linear dichroism at the Co K-edge was observed in the orthoaxial configuration, whereas it vanished in the axial orientation, thus spectroscopically confirming the crystal symmetry. Compounds Δ- and Λ- are shown to be enantiopure materials as evidenced by mirror-image natural circular dichroism spectra in the UV/vis in solution and in the X-ray range at the Co K-edge in single crystals. The surprising absence of detectable X-ray magnetic circular dichroism or X-ray magnetochiral dichroism signals at the Co K-edge, even at low temperature (3 K) and a high magnetic field (17 T), is ascribed to a strongly delocalized spin density on the tricobalt core.

摘要

采用一种基于阴离子交换的简单方法对扩展金属原子链（EMAC）[Co(dpa)(MeCN)]进行对映体拆分。使用手性盐（NBu）[As（酒石酸盐）]（Λ-或Δ-），可分别使EMAC对映体选择性结晶为Δ-Co(dpa)(MeCN)[Λ-As（酒石酸盐）]（Δ-）和Λ-Co(dpa)(MeCN)[Δ-As（酒石酸盐）]（Λ-），属于422空间群，而外消旋混合物生成[Co(dpa)(MeCN)][As（酒石酸盐）]·2MeCN（-），其结晶属于2/空间群。利用单晶中的多种二色性研究了EMAC对映体的局部电子和磁性结构。在正轴配置下，在Co K边观察到强烈的线性二色性，而在轴向配置中则消失，从而通过光谱证实了晶体对称性。化合物Δ-和Λ-被证明是对映体纯物质，这在溶液中的紫外/可见光谱以及单晶中Co K边的X射线范围内的镜像自然圆二色性光谱中得到了证明。令人惊讶的是，即使在低温（3 K）和高磁场（17 T）下，在Co K边也没有检测到X射线磁圆二色性或X射线磁手性二色性信号，这归因于三钴核上强烈离域的自旋密度。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/daa207c2aecd/c7sc04131d-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/c4e0185f9277/c7sc04131d-c1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/8881e614c914/c7sc04131d-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/c157094ae86c/c7sc04131d-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/e3ae737efcbc/c7sc04131d-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/ab3ef8cf3d03/c7sc04131d-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/354cda4ff814/c7sc04131d-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/daa207c2aecd/c7sc04131d-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/c4e0185f9277/c7sc04131d-c1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/8881e614c914/c7sc04131d-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/c157094ae86c/c7sc04131d-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/e3ae737efcbc/c7sc04131d-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/ab3ef8cf3d03/c7sc04131d-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/354cda4ff814/c7sc04131d-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d8d/5884025/daa207c2aecd/c7sc04131d-f5.jpg

相似文献

1
Enantiomeric resolution and X-ray optical activity of a tricobalt extended metal atom chain.三钴扩展金属原子链的对映体拆分与X射线光学活性
Chem Sci. 2017 Dec 4;9(5):1136-1143. doi: 10.1039/c7sc04131d. eCollection 2018 Feb 7.
2
Enantiopure Chiral Coordination Polymers Based on Polynuclear Paddlewheel Helices and Arsenyl Tartrate.基于多核桨轮螺旋体和酒石酸亚砷酸酯的对映体纯手性配位聚合物。
Polymers (Basel). 2018 Mar 13;10(3):311. doi: 10.3390/polym10030311.
3
Resolution, structures, and vibrational circular dichroism of helicoidal trinickel and tricobalt paddlewheel complexes.
Chirality. 2020 Jun;32(6):753-764. doi: 10.1002/chir.23211. Epub 2020 Mar 13.
4
New linear tricobalt complex of di(2-pyridyl)amide (dpa), [Co3(dpa)4(CH3CN)2][PF6]2.
Inorg Chem. 2000 Jul 10;39(14):3065-70. doi: 10.1021/ic000042o.
5
Induced chirality-at-metal and diastereoselectivity at Δ/Λ-configured distorted square-planar copper complexes by enantiopure Schiff base ligands: combined circular dichroism, DFT and X-ray structural studies.手性诱导在金属和Δ/Λ-手性扭曲的四面体型铜配合物中的对映选择性：手性席夫碱配体的圆二色性、DFT 和 X 射线结构研究的结合。
Dalton Trans. 2014 Feb 28;43(8):3313-29. doi: 10.1039/c3dt52871e.
6
Rapid Discrimination of Crystal Handedness by X-ray Natural Circular Dichroism (XNCD) Mapping.利用 X 射线自然圆二色性（XNCD）图谱快速区分手性晶体。
Chemistry. 2020 Oct 21;26(59):13363-13366. doi: 10.1002/chem.202001783. Epub 2020 Sep 21.
7
Solid-state to solution helicity inversion of pseudotetrahedral chiral copper(ii) complexes with 2,4-dihalo-salicylaldiminate ligands.具有2,4-二卤代水杨醛亚胺配体的假四面体手性铜（II）配合物的固态到溶液的螺旋度反转
Dalton Trans. 2020 Jun 23;49(24):8247-8264. doi: 10.1039/d0dt01649g.
8
Spontaneous resolution of a racemic nickel(II) complex and helicity induction via hydrogen bonding: the effect of chiral building blocks on the helicity of one-dimensional chains.外消旋镍（II）配合物的自发拆分及通过氢键诱导螺旋性：手性结构单元对一维链螺旋性的影响
Inorg Chem. 2008 Apr 7;47(7):2710-8. doi: 10.1021/ic7021424. Epub 2008 Feb 15.
9
Pseudotetrahedral Zn(II)-( or )-dihalogen-salicylaldiminato complexes with Λ- or Δ-chirality induction at-metal.在金属中心具有Λ-或Δ-手性诱导的假四面体Zn(II)-(或)-二卤代水杨醛亚胺配合物。
Dalton Trans. 2022 Feb 8;51(6):2385-2399. doi: 10.1039/d1dt04220c.
10
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.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。
Dalton Trans. 2009 Sep 14(34):6802-8. doi: 10.1039/b904081a. Epub 2009 Jul 7.

引用本文的文献

1
The Origin of Magnetic Anisotropy and Single-Molecule Magnet Behavior in Chromium(II)-Based Extended Metal Atom Chains.基于铬（II）的扩展金属原子链中磁各向异性和单分子磁体行为的起源
Inorg Chem. 2020 Feb 3;59(3):1763-1777. doi: 10.1021/acs.inorgchem.9b02994. Epub 2020 Jan 22.
2
Enantiopure Chiral Coordination Polymers Based on Polynuclear Paddlewheel Helices and Arsenyl Tartrate.基于多核桨轮螺旋体和酒石酸亚砷酸酯的对映体纯手性配位聚合物。
Polymers (Basel). 2018 Mar 13;10(3):311. doi: 10.3390/polym10030311.

本文引用的文献

1
Design and Study of Structural Linear and Nonlinear Optical Properties of Chiral [Fe(phen)] Complexes.手性[Fe(phen)]配合物的结构线性和非线性光学性质的设计与研究
Inorg Chem. 2018 Dec 3;57(23):14501-14512. doi: 10.1021/acs.inorgchem.8b01089. Epub 2018 Jun 20.
2
Spin Helicity in Chiral Lanthanide Chains.手性镧系链中的自旋螺旋度
Inorg Chem. 2016 Oct 17;55(20):10068-10074. doi: 10.1021/acs.inorgchem.6b01010. Epub 2016 Jul 13.
3
Strong magneto-chiral dichroism in a paramagnetic molecular helix observed by hard X-ray.通过硬X射线观察到顺磁性分子螺旋中的强磁手性二向色性。
Nat Phys. 2015 Jan 1;11(1):69-74. doi: 10.1038/nphys3152.
4
PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors.柏拉图挤压法：一种用于计算无序溶剂对计算得到的结构因子贡献的工具。
Acta Crystallogr C Struct Chem. 2015 Jan;71(Pt 1):9-18. doi: 10.1107/S2053229614024929. Epub 2015 Jan 1.
5
Chirality control of quadruple helixes of metal strings by peripheral chiral ligands.通过外围手性配体对金属链四重螺旋的手性控制。
Chem Asian J. 2014 Nov;9(11):3111-5. doi: 10.1002/asia.201402823. Epub 2014 Aug 21.
6
iotbx.cif: a comprehensive CIF toolbox.iotbx.cif：一个全面的CIF工具箱。
J Appl Crystallogr. 2011 Dec 1;44(Pt 6):1259-1263. doi: 10.1107/S0021889811041161. Epub 2011 Oct 29.
7
A short history of SHELX.SHELX简史。
Acta Crystallogr A. 2008 Jan;64(Pt 1):112-22. doi: 10.1107/S0108767307043930. Epub 2007 Dec 21.
8
Resolution of enantiomers in solution and determination of the chirality of extended metal atom chains.溶液中对映体的拆分及扩展金属原子链手性的测定。
Inorg Chem. 2007 Mar 5;46(5):1535-7. doi: 10.1021/ic062263l. Epub 2007 Feb 2.
9
Enantioseparation of extended metal atom chain complexes: unique compounds of extraordinarily high specific rotation.
Chirality. 2007 Mar;19(3):179-83. doi: 10.1002/chir.20355.
10
X-ray natural circular dichroism and chiral-EXAFS in gyrotropic crystals.
J Synchrotron Radiat. 2000 May 1;7(Pt 3):182-8. doi: 10.1107/S0909049500003009.