源自 N,N'-双(甘氨酰)吡咯烷二亚胺的二维镉(II)和锌(II)配位聚合物:微波辅助合成、结构、光谱特性及金属离子大小的影响。

IF 0.7 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY
Zheng Zhang, Lei Zhao, Hai Yan Yu, Hong Tao Zhang
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引用次数: 0

摘要

两种新型二维配位聚合物(CPs),即聚[diaqua[μ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O''':O'''']镉(II)],[Cd(C14H6N2O8)(H2O)2]n (1),以及聚[[四季[μ4-2,2'-(1,3,5,7-四氧杂-1,2,3,5,6,7-六氢吡咯并[3,4-f]异吲哚-2,6-二基)二乙酰氧基-κ4O:O':O'':O'''][μ2-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ2O:O']二水锌(II)],{[Zn(C14H6N2O8(H2O)2]-H2O}n (2),是由Cd(CH3COO)2-2H2O和Zn(CH3COO)2-2H2O通过微波辐照反应合成的、分别与 N,N'-双(甘氨酰)吡咯烷二亚胺{BGPD,即 2,2'-(1,3,5,7-四氧代-1,2,3,5,6,7-六氢吡咯并[3,4-f]异吲哚-2,6-二基)二乙酸,H2L}发生微波辐照反应而合成。在 1 的晶体结构中,CdII 离子由来自四个对称相关的 L2- 二离子的四个羧基 O 原子和两个配位水分子构成六配位,形成八面体配位几何结构。桥接的 L2- 二元离子将四个对称相关的 CdII 阳离子连接成一个具有 3,4 连接贝克斯拓扑结构的二维层状结构。在 2 的晶体结构中,ZnII 离子由来自三个不同 L2- 二元离子的三个羧基 O 原子和两个配位水分子五配位,形成了三叉双锥配位几何。两个晶体学上独立的配体分别作为 μ4- 和 μ2 桥连接 ZnII 离子,从而形成了一个具有 3,3 连接 hcb 拓扑结构的二维层。晶体结构分析表明,1 和 2 中吡咯烷二亚胺分子的两个羰基之间存在 n→π* 相互作用。与游离的 H2L 相比,CP 1 的荧光发射增强。2 的框架从 720 K 开始分解,这表明它具有很高的热稳定性。对基于 BGPD 配体的一系列结构进行的比较分析表明,由于立体效应的不同,金属离子的大小对金属离子的连接模式有很大的影响,这反过来又影响了 SBU(二级构建单元)和框架的结构。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
2D coordination polymers of cadmium(II) and zinc(II) derived from N,N'-bis(glycinyl)pyromellitic diimide: microwave-assisted synthesis, structures, spectroscopic properties and influence of metal-ion size.

Two new two-dimensional (2D) coordination polymers (CPs), namely, poly[diaqua[μ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O''']cadmium(II)], [Cd(C14H6N2O8)(H2O)2]n (1), and poly[[tetraaqua[μ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O'''][μ2-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ2O:O']dizinc(II)] dihydrate], {[Zn(C14H6N2O8(H2O)2]·H2O}n (2), have been synthesized by the microwave-irradiated reaction of Cd(CH3COO)2·2H2O and Zn(CH3COO)2·2H2O, respectively, with N,N'-bis(glycinyl)pyromellitic diimide {BGPD, namely, 2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetic acid, H2L}. In the crystal structure of 1, the CdII ion is six-coordinated by four carboxylate O atoms from four symmetry-related L2- dianions and two coordinated water molecules, furnishing an octahedral coordination geometry. The bridging L2- dianion links four symmetry-related CdII cations into a 2D layer-like structure with a 3,4-connected bex topology. In the crystal structure of 2, the ZnII ion is five-coordinated by three carboxylate O atoms from three different L2- dianions and two coordination water molecules, furnishing a trigonal bipyramidal coordination geometry. Two crystallographically independent ligands serve as μ4- and μ2-bridges, respectively, to connect the ZnII ions, thereby forming a 2D layer with a 3,3-connected hcb topology. Crystal structure analysis reveals the presence of n→π* interactions between two carbonyl groups of the pyromellitic diimide moieties in 1 and 2. CP 1 exhibits an enhanced fluorescence emission compared with free H2L. The framework of 2 decomposes from 720 K, indicating its high thermal stability. A comparative analysis of a series of structures based on the BGPD ligand indicates that the metal-ion size has a great influence on the connection modes of the metal ions due to different steric effects, which, in turn, affects the structures of the SBUs (secondary building units) and frameworks.

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来源期刊
Acta Crystallographica Section C Structural Chemistry
Acta Crystallographica Section C Structural Chemistry CHEMISTRY, MULTIDISCIPLINARYCRYSTALLOGRAPH-CRYSTALLOGRAPHY
CiteScore
1.60
自引率
12.50%
发文量
148
期刊介绍: Acta Crystallographica Section C: Structural Chemistry is continuing its transition to a journal that publishes exciting science with structural content, in particular, important results relating to the chemical sciences. Section C is the journal of choice for the rapid publication of articles that highlight interesting research facilitated by the determination, calculation or analysis of structures of any type, other than macromolecular structures. Articles that emphasize the science and the outcomes that were enabled by the study are particularly welcomed. Authors are encouraged to include mainstream science in their papers, thereby producing manuscripts that are substantial scientific well-rounded contributions that appeal to a broad community of readers and increase the profile of the authors.
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