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苦味酸根阴离子存在下铈(III)和钕(III)与五甘醇的配位:光谱和X射线结构研究

Coordination of Ce(III) and Nd(III) with pentaethylene glycol in the presence of picrate anion: spectroscopic and X-ray structural studies.

作者信息

Kusrini Eny, Saleh Muhammad Idiris, Lecomte Claude

机构信息

Department of Chemical Sciences, Faculty of Science and Technology, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2009 Sep 15;74(1):120-6. doi: 10.1016/j.saa.2009.05.024. Epub 2009 May 23.

Abstract

(1)H NMR evidence for direct coordination between the Ln(III) ion and the oxygen atoms of the pentaethylene glycol (EO5) ligand and the picrate anion (Pic) in [Ln(Pic)(2)(EO5)][Pic] {Ln=Ce and Nd} complexes are confirmed by single X-ray diffraction. No dissociation of Ln-O bonds in dimethyl sulfoxide-d solution was observed in NMR studies conducted at different temperatures ranging 25-100 degrees C. The Ln(III) ion was chelated to nine oxygen atoms from the EO5 ligand in a hexadentate manner and the two Pic anions in each bidentate and monodentate modes. Both compounds are isostructural and crystallized in monoclinic with space group P2(1)/c. Coordination environment around the Ce1 and Nd1 atoms can be described as tricapped trigonal prismatic and monocapped square antiprismatic geometries, respectively. The crystal packing of the complexes have stabilized by one dimensional (1D) chains along the [001] direction to form intermolecular O-Hcdots, three dots, centeredO and C-Hcdots, three dots, centeredO hydrogen bonding. The molar conductance of the complexes in DMSO solution indicated that both compounds are ionic. The complexes had a good thermal stability. Under the UV-excitation, these complexes exhibited the red-shift emission.

摘要

通过单晶X射线衍射证实了[Ln(Pic)₂(EO₅)][Pic] {Ln = Ce和Nd}配合物中Ln(III)离子与五乙二醇(EO₅)配体及苦味酸根阴离子(Pic)的氧原子之间直接配位的¹H NMR证据。在25至100℃的不同温度下进行的NMR研究中,未观察到二甲基亚砜-d溶液中Ln - O键的解离。Ln(III)离子以六齿方式与来自EO₅配体的九个氧原子螯合,两个Pic阴离子分别以双齿和单齿模式配位。两种化合物均为同构体,以单斜晶系P2(1)/c空间群结晶。Ce1和Nd1原子周围的配位环境分别可描述为三帽三棱柱和单帽四方反棱柱几何构型。配合物的晶体堆积通过沿[001]方向的一维(1D)链得以稳定,形成分子间O - H∙∙∙O和C - H∙∙∙O氢键。配合物在DMSO溶液中的摩尔电导率表明这两种化合物均为离子型。配合物具有良好的热稳定性。在紫外激发下,这些配合物表现出红移发射。

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