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首页> 外文期刊>Chemistry: A European journal >Polynuclear Complexes with Alkoxo and Phenoxo Bridges from In Situ Generated Hydroxy-Rich Schiff Base Ligands: Syntheses, Structures, and Magnetic Properties
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Polynuclear Complexes with Alkoxo and Phenoxo Bridges from In Situ Generated Hydroxy-Rich Schiff Base Ligands: Syntheses, Structures, and Magnetic Properties

机译：用原位生成的富羟基席夫碱配体与Alkoxo和Phenoxo桥形成多核配合物：合成，结构和磁性

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Complexes of new Schiff base ligands generated in situ from the reaction of 1-aminoglycerol, aldehydes, and metal ions are reported. [Cu_4- (HL~1)_4] (1) and [Ni_4O(HL~1)_3- (H_2O)_3)]·6H_2O·DMF·DMSO (2) have M_4O_4 cubane cores, with the L/M molar ratios of 4:4 and 3:4, respectively. [Mn~(III)_3Mn~(II)NaOCl_4(HL~1)_3]·3MeCN (3) has a unique pentanuclear trigonal propeller-shaped Mn~(III)_3Mn~(II)Na core structure, and the coordination assemblies are linked by hydrogen bonds to afford a 3D channel structure. [Cu_2- (HL~2)_2] (4) has a bis(μ_2-alkoxo)-bridged Cu_2O_2 core, with the binuclear species linked by hydrogen bonds to afford a 1D double-chain. [Ni_7(OH)_2- (OCH_3)_4(H_2L~3)_2(MeOH)_2(H_2O)_2]- (ClO_4)_2·10H_2O (5) has a heptanuclear structure containing heptadentate di- Schiff base ligands, with the nickel(II) ions bridged by phenoxo, alkoxo, hydroxo, and methoxo groups to afford a very rare face-sharing hexadruple defective cubane core with a Ni@Ni_6 arrangement. The lattice water molecules are linked by hydrogen bonds to form helical chains, which are further hydrogen- bonded to the coordination moieties to afford a 2D network. Variable temperature magnetic susceptibility measurements and nonlinear data-fitting revealed that the "2+4" type of cubane complex 1 shows medium intradimeric ferromagnetic interactions and weak interdimeric ferromagnetic interactions. For complexes 2 and 5, coexistent ferro- and antiferromagnetic couplings afford a non-zero spin ground state. However, compound 3 shows antiferromagnetic interactions between Mn~(III) and Mn~(II), and ferromagnetic interactions between the Mn~(III) centers, resulting in a global antiferromagnetic behavior. In conclusion, the reaction of 1-aminoglycerol with aldehydes and metal salts afforded polynuclear complexes with a rich structural diversity and remarkable magnetic behavior.
机译：报道了由1-氨基甘油，醛和金属离子反应原位生成的新席夫碱配体的配合物。 [Cu_4-（HL〜1）_4]（1）和[Ni_4O（HL〜1）_3-（H_2O）_3）]·6H_2O·DMF·DMSO（2）具有M_4O_4古巴核，摩尔比为L / M分别为4：4和3：4。 [Mn〜（III）_3Mn〜（II）NaOCl_4（HL〜1）_3]·3MeCN（3）具有独特的五核三角螺旋桨状Mn〜（III）_3Mn〜（II）Na核结构和配位体通过氢键连接以提供3D通道结构。 [Cu_2-（HL〜2）_2]（4）具有双（μ_2-烷氧基）桥联的Cu_2O_2核，双核物质通过氢键连接形成1D双链。 [Ni_7（OH）_2-（OCH_3）_4（H_2L〜3）_2（MeOH）_2（H_2O）_2]-（ClO_4）_2·10H_2O（5）具有包含七齿双席夫碱配体的七核结构，且由phenoxo，alkoxo，hydroxo和methoxo基团桥接的镍（II）离子提供了非常罕见的具有Ni @ Ni_6排列的面部共享六重缺陷型古巴核心。晶格水分子通过氢键连接形成螺旋链，进一步与配位部分氢键结合形成2D网络。可变温度磁化率测量和非线性数据拟合显示，“ 2 + 4”类型的古巴复合物1显示中等二聚体铁磁相互作用和弱二聚体铁磁相互作用。对于复合物2和5，同时存在的铁磁耦合和反铁磁耦合提供非零的自旋基态。然而，化合物3显示出Mn〜（III）和Mn〜（II）之间的反铁磁相互作用以及Mn〜（III）中心之间的铁磁相互作用，从而导致整体的反铁磁行为。总之，1-氨基甘油与醛和金属盐的反应提供了具有丰富的结构多样性和出色的磁行为的多核络合物。

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