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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Supramolecular metallomacrocycles based on trans-dicyanoferrite(III) building blocks: synthesis, crystal structure and magnetic properties
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Supramolecular metallomacrocycles based on trans-dicyanoferrite(III) building blocks: synthesis, crystal structure and magnetic properties

机译:基于反式双氰基铁氧体(III)构建单元的超分子金属大环化合物:合成,晶体结构和磁性

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摘要

The reaction of trans-[Fe(R-bpb)(CN)(2)](-)(R-bpb(2-)= R-substituted-1,2-bis(pyridine-2-carboxamido) benzenate) with trans- Mn(III) Schiff base complexes [Mn(5-X-saltn)]ClO4 (5-X-saltn(2-) = N,N'-propanolbis(5-X-substituted-salcylideneiminato) dianion) gave rise to cyanide-bridged neutral binuclear [MnFe] compounds [Mn(saltn)(MeOH)][Fe(bpb)(CN)(2)]center dot 3H(2)O ( 1), [Mn(saltn)(H2O)Fe(bpmb)(CN)(2)] center dot H2O (2), [Mn(saltn)(MeOH)Fe(bpClb)(CN)(2)]center dot 2H(2)O ( 3), and ionic [Mn2Fe](+)-[Fe](-) complexes [Mn-2(5-Br-saltn)(2)(H2O)(EtOH)Fe(bpb)(CN)(2)][Fe(bpb)(CN)(2)]center dot 6H(2)O ( 4) and [Mn-2(5-Cl-saltn)(2)(CH3OH)(EtOH)Fe(bpb)(CN)(2)][Fe(bpb)(CN)(2)]center dot 5H(2)O center dot MeCN (5). Four binuclear units of complexes 1-3 assemble in a head-to-tail way via hydrogen bonding giving rise to a metallo-supramolecular [MnFe](4) square, while two [Mn2Fe](+)-[Fe](-) units of complexes 4-5 form a metallo-supramolecular macrocyclic structure. Magnetic studies reveal that complexes 1-3 and 5 exhibit intermetallic ferromagnetic coupling, while complex 4 displays antiferromagnetic interaction between low-spin Fe(III) and high-spin Mn(III) through the cyanide bridges. Complexes 1, 4 and 5 display frequency dependent of current-alternating (ac) magnetic susceptibility, typical of the presence of slow magnetization relaxation. Because of the existence of intermolecular magnetic interaction, complex 4 shows an exchange-biased single-molecule magnet (SMM) behavior below 0.5 K.
机译:反式-[Fe(R-bpb)(CN)(2)](-)(R-bpb(2-)= R-取代的1,2,2-双(吡啶-2-甲酰胺基)苯甲酸酯)的反应反式Mn(III)Schiff碱络合物[Mn(5-X-saltn)] ClO4(5-X-saltn(2-)= N,N'-丙醇双(5-X-取代-salcylideneiminato)二价阴离子)氰化物桥接的中性双核[MnFe]化合物[Mn(saltn)(MeOH)] [Fe(bpb)(CN)(2)]中心点3H(2)O(1),[Mn(saltn)(H2O) Fe(bpmb)(CN)(2)]中心点H2O(2),[Mn(盐)(MeOH)Fe(bpClb)(CN)(2)]中心点2H(2)O(3)和离子[Mn2Fe](+)-[Fe](-)络合物[Mn-2(5-Br-盐)(2)(H2O)(EtOH)Fe(bpb)(CN)(2)] [Fe(bpb) (CN)(2)]中心点6H(2)O(4)和[Mn-2(5-Cl-盐)(2)(CH3OH)(EtOH)Fe(bpb)(CN)(2)] [ Fe(bpb)(CN)(2)]中心点5H(2)O中心点MeCN(5)。配合物1-3的四个双核单元通过氢键从头到尾的方式组装,从而形成金属-超分子的[MnFe](4)正方形,而两个[Mn2Fe](+)-[Fe](-)配合物4-5的单元形成金属-超分子大环结构。磁性研究表明,配合物1-3和5表现出金属间铁磁耦合,而配合物4通过氰化物桥显示出低自旋Fe(III)和高自旋Mn(III)之间的反铁磁相互作用。配合物1、4和5显示的频率取决于电流交变(ac)磁化率,这是慢磁化弛豫的典型代表。由于存在分子间磁性相互作用,复合物4在0.5 K以下显示出交换偏置的单分子磁体(SMM)行为。

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