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基于5-官能化间苯二甲酸和联吡啶的一系列锌配位聚合物的组装

Assembly of a series of zinc coordination polymers based on 5-functionalized isophthalic acids and dipyridyl.

作者信息

Wang Tao, Zhu Rong-Rong, Zhang Xiao-Feng, Yan Tong, Wang Quan, Feng Jing, Zhou Jie, Du Lin, Zhao Qi-Hua

机构信息

Key Laboratory of Medicinal Chemistry for Natural Resource Education Ministry, School of Chemical Science and Technology - Pharmacy, Yunnan University Kunming 650091 PR China

出版信息

RSC Adv. 2018 Feb 16;8(14):7428-7437. doi: 10.1039/c7ra12874f. eCollection 2018 Feb 14.

Abstract

To investigate the influence of different 5-functionalized isophthalate ligands on the self-assembly and structures of Zn(ii)-based coordination polymers (CPs), we selected four 5-functionalized isophthalate ligands coordinated with 4,4'-bipyridyl (bpy) and Zn(ii) salt, and four new CPs, namely, {[Zn(EtOip)(bpy)]·2HO} (1), {[Zn(PrOip)(bpy)]·2HO} (2), [Zn( BuOip)(bpy)] (3) and [Zn( PeOip)(bpy)] (4) (where EtOip = 5-ethoxyisophthalate, PrOip = 5--propoxyisophthalate, BuOip = 5--butoxyisophthalate and PeOip = 5--pentyloxyisophthalate), were prepared under hydrothermal conditions. Moreover, we considered changing the features of the N-ligands (length), which are expected to alter the structural diversities and properties of the resultant CPs. We used 1,2-bis(4-pyridyl)ethene (bpe) to replace bpy; and obtained four new coordination polymers (CPs), namely, {[Zn(EtOip)(bpe)]·HO} (5), {[Zn(PrOip)(bpe)]·HO} (6), {[Zn( BuOip)(bpe)]·0.5DMF} (7) and [Zn( PeOip)(bpe)] (8). All of these compounds were characterized by single crystal X-ray diffraction, infrared spectroscopy, elemental analysis and powder X-ray diffraction measurements. Single-crystal X-ray analysis reveals that the structure of complexes 1-4 are very similar, although different functionalized-isophthalate ligands are employed. Complexes 5, 6 and 7 possess a two-dimensional (2D) layered structure, and the 2D framework of complexes 5 and 7 can be rationalized to be a threefold interpenetrating four-connected {4·6} topological network, while 6 exhibits a twofold interpenetrating 4-connected 2D framework. Compound 8 features a 6-connected 3D topology net based on a novel bimetallic unit [(Zn)(CO)] linked by mixed PeOip and bpe ligands. Moreover, thermal and photoluminescence properties of the synthesized complexes were also studied in detail.

摘要

为了研究不同的5-官能化间苯二甲酸酯配体对锌(II)基配位聚合物(CPs)自组装和结构的影响,我们选择了四种5-官能化间苯二甲酸酯配体与4,4'-联吡啶(bpy)和锌(II)盐配位,并在水热条件下制备了四种新型CPs,即{[Zn(EtOip)(bpy)]·2H₂O} (1)、{[Zn(PrOip)(bpy)]·2H₂O} (2)、[Zn(ⁿBuOip)(bpy)] (3) 和 [Zn(ⁿPeOip)(bpy)] (4)(其中EtOip = 5-乙氧基间苯二甲酸酯,PrOip = 5-ⁿ-丙氧基间苯二甲酸酯,ⁿBuOip = 5-ⁿ-丁氧基间苯二甲酸酯,ⁿPeOip = 5-ⁿ-戊氧基间苯二甲酸酯)。此外,我们考虑改变N-配体的特征(长度),预计这会改变所得CPs的结构多样性和性质。我们用1,2-双(4-吡啶基)乙烯(bpe)取代bpy,得到了四种新型配位聚合物(CPs),即{[Zn(EtOip)(bpe)]·H₂O} (5)、{[Zn(PrOip)(bpe)]·H₂O} (6)、{[Zn(ⁿBuOip)(bpe)]·0.5DMF} (7) 和 [Zn(ⁿPeOip)(bpe)] (8)。所有这些化合物都通过单晶X射线衍射、红外光谱、元素分析和粉末X射线衍射测量进行了表征。单晶X射线分析表明,尽管使用了不同的官能化间苯二甲酸酯配体,但配合物1-⁴的结构非常相似。配合物5、6和7具有二维(2D)层状结构,配合物5和7的2D框架可以合理化为三重互穿的四连接{4·6}拓扑网络,而6表现出双重互穿的4连接2D框架。化合物8具有基于由混合的ⁿPeOip和bpe配体连接的新型双金属单元[(Zn)₂(CO₃)]的6连接3D拓扑网络。此外,还详细研究了合成配合物的热性能和光致发光性能。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9aea/9078387/51a8eba10855/c7ra12874f-f1.jpg

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