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首页> 外文期刊>Crystal growth & design >Polynuclear complexes of ligands containing in situ formed oxazinane and oxazolidine rings with appended alkoxyl and phenol groups
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Polynuclear complexes of ligands containing in situ formed oxazinane and oxazolidine rings with appended alkoxyl and phenol groups

机译：含有原位形成的恶嗪烷和恶唑烷环并带有附加的烷氧基和酚基的配体的多核配合物

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摘要

In situ formation of ligands is an efficient approach to synthesizing novel complexes with unique coordinating moieties. Oxazolidines and oxazinanes are 1,3-N,O-containing five-membered and six-membered heterocycles, respectively. Metal complexes of ligands derived from these two heterocycles are rather rare. In this work, we designed and synthesized a novel multihydoxy ligand, 2-((2,3-dihydroxypropylamino)methyl)phenol (H _3L ~1). It contains both aminoethanol and aminopropanol units, which may be employed to react with aldehydes to afford oxazolidines and oxazinanes, respectively. Thus, H _3L ~1 was reacted with metal salts in the absence or presence of aldehydes to afford complexes [Cu(HL ~1)] _2 (1), [CuL ~2] _4?4CH _3OH (2) [Zn _5Na _2(L ~3) _4(DMSO) _(2.65)(DMF) _(1.35)]?DMF (3), and [Ni(HL ~4)] _2 (4). Complex 1 is a dialkoxo-bridged binuclear Cu(II) complex. The coordination moieties are linked by intermolecular C-H???O hydrogen bonds to afford a 1D double-chain supramolecular structure. Interestingly, in complexes 2-4, H ~3L _1 has been reacted with formaldehyde, salicylaldehyde, and 2,6-diformyl-4-cresol to afford novel ligands H _2L ~2, H _3L ~3, and H _3L ~4, respectively. The combination of in situ formed oxazinane or oxazolidine rings with appended alkoxyl and phenol functionalities in these ligands has been demonstrated to form a rich diversity of coordination structures. Thus, 2 is a tetranuclear Cu(II) complex with a face-sharing double defective cubane core structure. In this complex, (L ~2) ~(2-) ligands coordinate in two different bridging modes with the Harris notations of 3.1 _12 _(12)2 _(13)1 _1 and 3.1 _13 _(123)1 _11 _1, respectively. Complex 3 has an interesting heptanuclear Zn _5Na _2 core structure. A central Zn(II) is coordinated with four alkoxo O atoms from four (L ~3) ~(3-) ligands. Each of the O atom further bridges another Zn(II) atom, resulting in a Zn _5 moiety, which is then connected to two Na ~+ by phenoxo O bridges, finally affording the Zn _5Na _2 core. The bridging mode of (L ~3) ~(3-) can be designated as 4.2 _(12)2 _(13)1 _13 _(124)1 _1. And Complex 4 is a binuclear Ni(II) complex containing di-μ _2-phenoxo bridges. The coordination moieties are linked by intermolecular C-H???π, C-H???O, and π???π interactions to afford a two-dimensional supramolecular network. These results indicate that the combination of in situ formed oxazinane and oxazolidine rings with appended phenol and alkoxyl functionalities is an efficient approach to developing novel ligands and complexes with a rich structural diversity. Variable temperature magnetic data measurements revealed that medium antiferromagnetic interaction exists between the Cu(II) centers in complex 1 with a -2J value of 278 cm ~(-1). And in complex 4, weak antiferromagnetic coupling occurs between the Ni(II) centers, with a -2J value of 9.36 cm ~(-1).
机译：配体的原位形成是合成具有独特配位部分的新型复合物的有效方法。恶唑烷和恶嗪酮分别是含1，3-N，O的五元和六元杂环。衍生自这两个杂环的配体的金属络合物非常罕见。在这项工作中，我们设计并合成了一种新型的多羟基配体2-（（2,3-二羟丙基氨基）甲基）苯酚（H _3L〜1）。它同时包含氨基乙醇和氨基丙醇单元，可用于与醛反应，分别提供恶唑烷和恶嗪酮。因此，在不存在或存在醛的情况下，使H _3L〜1与金属盐反应，生成配合物[Cu（HL〜1）] _2（1），[CuL〜2] _4？4CH _3OH（2）[Zn _5Na _2 （L〜3）_4（DMSO）_（2.65）（DMF）_（1.35）]？DMF（3）和[Ni（HL〜4）] _2（4）。配合物1是二恶英桥联的双核Cu（II）配合物。配位部分通过分子间的C H H O氢键连接，从而提供一维双链超分子结构。有趣的是，在配合物2-4中，H〜3L _1已与甲醛，水杨醛和2,6-二甲酰-4-甲酚反应，得到新的配体H _2L〜2，H _3L〜3和H _3L〜4，分别。已经证明在这些配体中原位形成的恶嗪烷或恶唑烷环与附加的烷氧基和苯酚官能团的结合形成了丰富的配位结构多样性。因此，2是具有面共享双缺陷古巴核心结构的四核Cu（II）配合物。在这种复合物中，（L〜2）〜（2-）配体在两种不同的桥接模式下以3.1 _12 _（12）2 _（13）1 _1和3.1 _13 _（123）1 _11 _1的哈里斯符号进行配位，分别。配合物3具有有趣的七核Zn _5Na _2核心结构。中心的Zn（II）与来自四个（L〜3）〜（3-）配体的四个烷氧基O原子配位。每个O原子进一步桥接另一个Zn（II）原子，得到Zn _5部分，然后通过phenoxo O桥将其连接到两个Na〜+，最后得到Zn _5Na _2核心。 （L〜3）〜（3-）的桥接模式可以指定为4.2 _（12）2 _（13）1 _13 _（124）1 _1。配合物4是包含di-μ_2-phenoxo桥的双核Ni（II）配合物。配位部分通过分子间的C-HHπ，C-HHO和π???π相互作用连接在一起，得到二维的超分子网络。这些结果表明，原位形成的恶嗪烷和恶唑烷环与附加的苯酚和烷氧基官能团的结合是开发具有丰富结构多样性的新型配体和配合物的有效方法。可变温度的磁数据测量表明，复合物1中的Cu（II）中心之间存在中等反铁磁相互作用，其-2J值为278 cm〜（-1）。在络合物4中，Ni（II）中心之间发生弱的反铁磁耦合，其-2J值为9.36 cm〜（-1）。

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