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首页> 外文期刊>Crystal growth & design >Carbophosphazene-based multisite coordination ligands: Metalation studies on the pyridyloxy carbophosphazene, [NC(NMe_2)]_2[NP(p- OC_5H_4N)_2]
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Carbophosphazene-based multisite coordination ligands: Metalation studies on the pyridyloxy carbophosphazene, [NC(NMe_2)]_2[NP(p- OC_5H_4N)_2]

机译:基于碳磷腈的多位配位配体:吡啶氧基碳磷腈[NC(NMe_2)] _ 2 [NP(p- OC_5H_4N)_2]的金属化研究

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摘要

Thepyridyloxycarbophosphazene, [NC(NMe_2)]_2-[NP(p- OC_5H_4N)_2] (L), reacted with Cd(OAc) _2-4H_2O to afford a rail-road-like double-strand coordination polymer, [{Cd(CH_3COO)2(L)}(CH _3OH)(H_2O)_2]_n (1). The crystal structure of 1 reveals that L functions as a bridging ligand to link successive cadmium atoms. Two such parallel-running strands are further interconnected by actetate bridging ligands forming Cd_2O_2 four-membered connections. The double-stranded coordination polymer is taken into the second dimension by intermolecular hydrogen bonding between the oxygen atoms of the acetate bridge and a tetrameric water cluster. Interaction of L with Cd(NO _3)_2-4H_2O leads to the formation of [Cd(NO _3)_2(L)(MeOH)]_n (2). In the presence of pyridine (Py), this reaction affords [Cd(NO_3)_2 (L)(Py) _2]_n (3). In contrast to 1, compounds 2 and 3 are single-strand one-dimensional (1-D) coordination polymers. In 1-3, the cadmium atoms are seven-coordinate in a pentagonal-bipyramidal geometry. The reaction of L with ZnCl_2, MnCl_2, or CoCl_2 leads to the formation of [{Zn(Cl)_2(L)}(MeOH)]_n (4), [Mn(Cl) _2(L)_2]_n (5), and [CoCl)_2(L) _2]n (6). Structure 4 is a simple 1-D coordination polymer containing tetrahedral zinc atoms, while 5 and 6 are macrocycle-linked coordination polymers. In the latter, successive metal atoms are linked by a pair of carbophosphazene ligands to generate 24-membered macrocyclic rings which are interconnected to each other at the metal center to afford the coordination polymer chain.
机译:吡啶氧基氧羰基磷腈[NC(NMe_2)] _ 2- [NP(p-OC_5H_4N)_2](L)与Cd(OAc)_2-4H_2O反应,得到类似铁路的双链配位聚合物[[{Cd( CH_3COO)2(L)}(CH _3OH)(H_2O)_2] _n(1)。 1的晶体结构表明L充当桥接配体以连接连续的镉原子。两条这样的平行运行的链进一步通过乙酸桥键配体相互连接,形成Cd_2O_2四元连接。通过在乙酸酯桥的氧原子和四聚体水簇之间的分子间氢键将双链配位聚合物带入第二维。 L与Cd(NO _3)_2-4H_2O的相互作用导致形成[Cd(NO _3)_2(L)(MeOH)] _ n(2)。在吡啶(Py)的存在下,该反应得到[Cd(NO_3)_2(L)(Py)_2] _n(3)。与1相反,化合物2和3是单链一维(1-D)配位聚合物。在1-3中,镉原子在五角双锥体中为七个坐标。 L与ZnCl_2,MnCl_2或CoCl_2的反应导致形成[{Zn(Cl)_2(L)}(MeOH)] _ n(4),[Mn(Cl)_2(L)_2] _n(5 )和[CoCl)_2(L)_2] n(6)。结构4是包含四面体锌原子的简单的1-D配位聚合物,而5和6是大环连接的配位聚合物。在后者中,连续的金属原子通过一对碳磷腈配体连接以生成24元大环,该环在金属中心相互连接以提供配位聚合物链。

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