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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Structural diversity and magnetic properties of six metal–organic polymers based on semirigid tricarboxylate ligand of 3,5-bi(4-carboxyphenoxy)-benzoic acid
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Structural diversity and magnetic properties of six metal–organic polymers based on semirigid tricarboxylate ligand of 3,5-bi(4-carboxyphenoxy)-benzoic acid

机译:基于3,5-二(4-羧基苯氧基)-苯甲酸的半刚性三羧酸酯配体的六种金属有机聚合物的结构多样性和磁性

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摘要

Solvothermal reactions of the semirigid 3,5-bi(4-carboxyphenoxy)benzoic acid (H_3BCP) and transitional metal cations with the help of three ancillary bridging imidazole linkers afforded six coordination polymers, namely, [Co(HBCP)(1,4-bib)_(0.5)]n (1), {[Mn_(1.5)(BCP)(1,4-bib)_(0.5)(μ2-H_2O)(H_2O)_2]·(1,4-bib)_(0.5)}_n (2), {[Mn_(0.5)(1,4-bib)(H_2O)]·(H_2BCP)}_n (3), {[Fe(BCP)_(0.5)(HCOO)_(0.5)(4,4’-bibp)_(0.5)]·2H_2O}_n (4), [Ni_(2.5)(HBCP)(BCP) (4,4’-bibp)_2(μ_2-H_2O)(H_2O)_2]_n (5), and [Ni(HBCP)(1,4-bidb)_(1.5)(H_2O)_2]_n (6), (1,4-bib = 1,4-bis(1H-imidazol-4-yl)benzene, 1,4-bidb = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene, 4,4’-bibp = 4,4’-bis(imidazol-1-yl)-biphenyl). Their structures and properties were determined by single-crystal and powder X-ray diffraction analyses, IR spectra, elemental analyses, thermogravimetric analyses (TGA), and X-ray photoelectron spectroscopy (XPS). Complex 1 displays unusual 2D + 2D→2D parallel entangled networks consisting of (3,4)-connected 3,4L83 sheets. Complex 2 exhibits an interesting 2-fold interpenetrated framework with a trinodal (4,4,6)-connected (3·4·5·6~2·7)_2(3·6·7~4)_2(3~2·4~2·5~2·6~2·7~6·9) topology. The host network of complex 3 is a 2D 4-connected (4~4·6~2)-sql sheet. Complex 4 affords unprecedented 3D (4,6,6)-coordinated framework with point symbol of (4~5·6)(4~8·6~7)(4~9·6~3·8~3)_2, in which the 1D helix water chains occupy the void channels. Complex 5 can be regarded as a novel self-penetrating (4,4,4,5)-coordinated framework with point symbol of (4·5~4·6)_2(4·6~5·7·8~3)_2(5·6·7·8~3)_2(5~2·8~3·9~2), which contains two interpenetrated (3,4,4,5)-coordinated (4·5~4·6)_2(4·6~5·7·8~3)_2(5·6·7)_2(5~2·8~3·9~2) subnets linked by μ_2-H_2O. Complex 6 shows a 1D ladder chain, which are further assembled into a 3D supramolecular structure via O–H?O and π?π interactions. Moreover, magnetic studies indicate that both complex 2 and 4 show antiferromagnetic properties.
机译:半刚性的3,5-双(4-羧基苯氧基)苯甲酸(H_3BCP)与过渡金属阳离子的溶剂热反应借助三个辅助桥联咪唑连接基提供了六种配位聚合物,即[Co(HBCP)(1,4- bib)_(0.5)] n(1),{[Mn_(1.5)(BCP)(1,4-bib)_(0.5)(μ2-H_2O)(H_2O)_2]·(1,4-bib) _(0.5)} _ n(2),{[Mn_(0.5)(1,4-bib)(H_2O)]·(H_2BCP)} _ n(3),{[Fe(BCP)_(0.5)(HCOO) _(0.5)(4,4'-bibp)_(0.5)]·2H_2O} _n(4),[Ni_(2.5)(HBCP)(BCP)(4,4'-bibp)_2(μ_2-H_2O) (H_2O)_2] _n(5)和[Ni(HBCP)(1,4-bidb)_(1.5)(H_2O)_2] _n(6),(1,4-bib = 1,4-bis( 1H-咪唑-4-基)苯,1,4-bidb = 1,4-双(1-咪唑基)-2,5-二甲基苯,4,4'-bibp = 4,4'-双(咪唑-1-基)-联苯)。通过单晶和粉末X射线衍射分析,IR光谱,元素分析,热重分析(TGA)和X射线光电子能谱(XPS)确定了它们的结构和性质。复合体1显示不寻常的2D + 2D→2D并行纠缠网络,该网络由(3,4)连接的3,4L83张组成。复合体2展示了一个有趣的2倍互穿框架,其中三节点(4,4,6)连接(3·4·5·6〜2·7)_2(3·6·7〜4)_2(3〜2) ·4〜2·5〜2·6〜2·7〜6·9)拓扑。复合体3的主机网络是2D 4连接的(4〜4·6〜2)-sql表。复杂物4提供了前所未有的3D(4,6,6)坐标框架,其点符号为(4〜5·6)(4〜8·6〜7)(4〜9·6〜3·8〜3)_2,其中一维螺旋水链占据了空通道。配合物5可以看作是一种新颖的自穿透(4,4,4,5)协调的框架,其点符号为(4·5〜4·6)_2(4·6〜5·7·8〜3) _2(5·6·7·8〜3)_2(5〜2·8〜3·9〜2),其中包含两个互穿的(3,4,4,5)坐标(4·5〜4·6) )_2(4·6〜5·7·8〜3)_2(5·6·7)_2(5〜2·8〜3·9〜2)子网由μ_2-H_2O链接。配合物6显示一维梯形链,通过O–H2O和π?π相互作用进一步组装成3D超分子结构。此外,磁性研究表明,配合物2和4均显示反铁磁性质。

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