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首页> 外文期刊>Crystal growth & design >Crystal Engineering Applied to Modulate the Structure and Magnetic Properties of Oxamate Complexes Containing the [Cu(bpca)](+) Cation
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Crystal Engineering Applied to Modulate the Structure and Magnetic Properties of Oxamate Complexes Containing the [Cu(bpca)](+) Cation

机译：晶体工程应用于调节含[Cu（bpca）]（+）阳离子的草酸盐配合物的结构和磁性

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摘要

This work deals with the crystal engineering features of four related copper(II)-based compounds with formulas {[{Cu(bpca)}(2)(H(2)ppba)]center dot 1.33DMF center dot 0.66DMSO}(n) (2), [{Cu(bpca)(H2O)}(2)(H(2)ppba)] (3), [{Cu(bpca)}(2)(H(2)ppba)]center dot DMSO (4), and [{Cu(bpca)}(2)(H(2)ppba)]center dot 6H(2)O (5) [H(4)ppba = N,N'-1,4-phenylenebis(oxamic acid) and Hbpca = bis(2-pyridylcarbony1)amide] and how their distinct molecular and crystal structures translate into their different magnetic properties. 2 and 3 were obtained through the hydrolytic reaction of the double-stranded oxamato-based dipalladium(II) paracydophane precursor of formula [{K-4(H2O)(2)}{Pd-2(ppba)(2)}] (1) with the mononuclear copper(II) complex [Cu(bpca)(H2O)(2)](+), either in a water-DMSO-DMF solvent mixture or in water, respectively. The straightforward reaction of the neutral atppba molecule with [Cu(bpca)(H2O)(2)](+) in a water-DMSO mixture afforded compound 4, whereas compound 5 resulted from the reaction between the copper(II) complex and the Icppba salt in water. The [Pd-2(ppba)(2)](4-) tetraanionic unit which is present in 1 has a [3,3] metallacyclophane-type motif connected by two N-Pd-N bonds. This entity acts as a ligand toward partially hydrated potassium(I) cations through its outer oxamate oxygens leading to a neutral three-dimensional network. The structure of 2 consists of neutral chains made up of double oxo(carboxylate-oxamate)-bridged diRbis(2-pyridylcarbonyl)amidate}copper(II)] units are which connected by the extended H(2)ppba(2-) ligand, each of its oxamate fragments adopting a bidentate/outer monodentate coordination anode. Compounds 2-5 are neutral and centrosymmetric dicopper(II) complexes which have in common the presence of peripheral bpca ligands and H(2)ppba(2-) as a bridge with each of its monoprotonated oxamate groups exhibiting rare monodentate (3) and bis-bidentate (4 and 5) coordination modes. Compounds 2, 4, and 5 share the same basic [{Cu(bpca)}(2)(H(2)ppba)] unit, but besides the difference in the cocrystallization solvent molecules and synthetic strategies, they feature very different crystal structures. To better understand the role of palladium(II) ions in the formation of 2 and 3, some studies were carried out using different mixtures of solvents such as water, DMSO, and DMF which revealed a major importance of DMF in the formation of 2 and the dependence on the palladium(II) ions in the formation of 3. A reaction pathway leading to the formation of 2 and 3 is then proposed. The variable-temperature (2.0-300 K) magnetic susceptibility measurements of 2, 4, and 5 revealed the occurrence of weak ferro- [J = +0.70 cm(-1) (2)] and antiferromagnetic interactions [J=-0.90 (4) and -0.79 cm(-1) (5)], the spin Hamiltonian being defined as H =-JS(1).S-2. The different nature and strength of the magnetic coupling along this unique series of compounds are discussed in the light of the structural data, and they are compared with those of related dicopper (II) systems.
机译：这项工作处理的四个相关的基于化学式为{[{Cu（bpca）}（2）（H（2）ppba）]的中心点1.33DMF中心点0.66DMSO}（n ）（2），[{Cu（bpca）（H2O）}（2）（H（2）ppba）]（3），[{Cu（bpca）}（2）（H（2）ppba）]中心点DMSO（4）和[{Cu（bpca）}（2）（H（2）ppba）]中心点6H（2）O（5）[H（4）ppba = N，N'-1,4-亚苯基双（草酰胺酸）和Hbpca =双（2-吡啶基羰基）酰胺，以及它们不同的分子和晶体结构如何转化为不同的磁性。通过式[{K-4（H2O）（2）} {Pd-2（ppba）（2）}]的双链基于草胺基的二钯（II）对环十二烷前体的水解反应获得2和3 1）分别在水-DMSO-DMF溶剂混合物中或在水中使用单核铜（II）配合物[Cu（bpca）（H2O）（2）]（+）。在水-DMSO混合物中，中性atppba分子与[Cu（bpca）（H2O）（2）]（+）的直接反应提供了化合物4，而化合物5是由铜（II）配合物与三价铜之间的反应产生的Icppba盐在水中。存在于1中的[Pd-2（ppba）（2）]（4-）四阴离子单元具有通过两个N-Pd-N键连接的[3，3]金属杂环基型基序。该实体通过其外部草酸盐氧作为部分水合的钾（I）阳离子的配体，导致形成中性的三维网络。 2的结构由中性链组成，该中性链由双氧代（羧酸根-草酸酯）桥联的diRbis（2-吡啶基羰基）氨基酸酯}铜（II）]单元组成，并通过扩展的H（2）ppba（2-）配体连接，其每个草酸盐碎片均采用双齿/外单齿配位阳极。化合物2-5是中性和向心对称的dicopper（II）络合物，它们共同存在外围bpca配体和H（2）ppba（2-）作为桥联，其每个单质子化草酸酯基团均显示稀有的单齿（3）和双双（4和5）协调模式。化合物2、4和5共享相同的基本[{Cu（bpca）}（2）（H（2）ppba）]单元，但除了共结晶溶剂分子和合成策略不同外，它们的晶体结构也非常不同。为了更好地理解钯（II）离子在2和3形成中的作用，使用不同的溶剂混合物（例如水，DMSO和DMF）进行了一些研究，这些研究表明DMF在2和3形成中的重要作用。依赖于形成3中的钯（II）离子。然后提出了导致2和3形成的反应途径。对2、4和5的温度变化（2.0-300 K）的磁化率测量表明，弱铁的发生[J = +0.70 cm（-1）（2）]和反铁磁相互作用[J = -0.90（ 4）和-0.79 cm（-1）（5）]，自旋哈密顿量定义为H = -JS（1）.S-2。根据结构数据讨论了沿着这种独特系列化合物的磁耦合的不同性质和强度，并将它们与相关的双铜（II）系统进行了比较。

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