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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Magneto-structural versatility of copper(II)-3-phenylpropionate coordination polymers with N-donor coligands
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Magneto-structural versatility of copper(II)-3-phenylpropionate coordination polymers with N-donor coligands

机译：铜（II）-3-苯基丙酸铜（N）-配体与配体的磁结构多功能性

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摘要

A novel series of copper(II) coordination polymers [Cu-2(O2CC8H9)(4)(pyz)](n) (1), [Cu-2(O2CC8H9)(4)(dps)](n) (2), {[Cu(O2CC8H9)(2)(dps)(H2O)]center dot H2O}(n) (3), {[NaCu(O2CC8H9)(2)(bpm)(NO3)]center dot H2O}(n) (4), and [Cu-4(O2CC8H9)(6)-(OH)(2)(bpp)(2)](n) (5) [O2CC8H9- = 3-phenylpropionate anion, pyz = pyrazine, dps = di(4-pyridyl)sulfide, bpm = 2,2'-bipyrimidine, and bpp = 1,3-bis(4-pyridyl)propane] have been synthesized and magneto-structurally investigated. Compounds 1 and 2 belong to a large group of copper(II) carboxylates where bis-monodentate pyz (1) and dps (2) ligands connect the paddle-wheel [Cu-2(II)(mu-O2CC8H9)(4)] units leading to alternating copper(II) chains. The structure of 3 consists of uniform chains of trans-[Cu-II(O2CC8H9)(2)] units linked by the bis-monodentate dps ligand. Compound 4 consists of heterobimetallic chains where [(Na2Cu2II)-Cu-I(mu-O2CC8H9)(4)(NO3)(2)] units are doubly bridged by bis-bidentate bpm ligands. Compound 5 is also a chain compound whose structure is made up by tetranuclear [Cu-4(II)(mu(3)-OH)(2)(mu-O2CC8H9)(4)(O2CC8H9)(2)] units which are doubly bridged by bis-monodentate bpp ligands. The magnetic properties were investigated in the temperature range 1.8-300 K. Strong antiferromagnetic interactions across the quadruple syn-syn carboxylate are observed in 1 and 2 [J = -378 (1) and -348 cm(-1) (2)] whereas a weak ferromagnetic coupling through the double out-of-plane oxo(carboxylate) bridge occurs in 4 [J = +2.66 cm(-1)], the spin Hamiltonian being defined as H = -JS(1).S-2 with S-1 = S-2 = S-Cu = 1/2. A quasi Curie law is observed for 3 (theta = -0.36 cm(-1)), the bis-monodentate dps ligand being a very poor mediator of magnetic interactions. The analysis of the magnetic properties of 5 is quite complex because of the presence of two crystallographically independent tetracopper(II) units with single-mu-hydroxo, di-mu-hydroxo, mu(3)-hydroxo and single-mu-hydroxo plus double syn, syn carboxylate bridges in each one. The nature and values of the magnetic couplings for 5 obtained by fitting (intermediate, strong and weak antiferromagnetic interactions for the three former exchange pathways respectively, and intermediate ferromagnetic interactions for the latter one) were substantiated by DFT type calculations.
机译：一系列新型的铜（II）配位聚合物[Cu-2（O2CC8H9）（4）（pyz）]（n）（1），[Cu-2（O2CC8H9）（4）（dps）]（n）（2 ），{[Cu（O2CC8H9）（2）（dps）（H2O）]中心点H2O}（n）（3），{[NaCu（O2CC8H9）（2）（bpm）（NO3）]中心点H2O}（ n）（4）和[Cu-4（O2CC8H9）（6）-（OH）（2）（bpp）（2）]（n）（5）[O2CC8H9- = 3-苯基丙酸根阴离子，pyz =吡嗪，已经合成了dps =二（4-吡啶基）硫化物，bpm = 2,2'-联嘧啶，bpp = 1,3-双（4-吡啶基）丙烷]，并进行了磁结构研究。化合物1和2属于一大类羧酸铜（II），其中双单齿pyz（1）和dps（2）配体连接明轮[Cu-2（II）（mu-O2CC8H9）（4）]导致交替的铜（II）链的单元。 3的结构由通过双单齿dps配体连接的反式[[Cu-II（O2CC8H9）（2）]]单元的均匀链组成。化合物4由杂双金属链组成，其中[（Na2Cu2II）-Cu-I（mu-O2CC8H9）（4）（NO3）（2）]单元由双双bpm配体双桥连接。化合物5也是一种链状化合物，其结构由四核[Cu-4（II）（mu（3）-OH）（2）（mu-O2CC8H9）（4）（O2CC8H9）（2）]单元组成由双单齿bpp配体双桥连接。在1.8-300 K的温度范围内研究了磁性。在1和2中观察到跨四重顺式羧酸盐的强反铁磁相互作用[J = -378（1）和-348 cm（-1）（2）]而通过双重平面外氧代（羧酸根）桥的弱铁磁耦合在4 [J = +2.66 cm（-1）]中发生，自旋哈密顿量定义为H = -JS（1）.S-2其中S-1 = S-2 = S-Cu = 1/2准居里定律观察到3（θ= -0.36 cm（-1）），双单齿dps配体是磁相互作用的非常差的介体。 5的磁性分析非常复杂，因为存在两个晶体学独立的四铜（II）单元，分别带有单mu-羟基，di-mu-羟基，mu（3）-羟基和单个mu-羟基加上每个中有两个syn，syn羧酸盐桥。通过DFT类型计算证实了通过拟合获得的5个磁耦合的性质和值（分别针对前三个交换路径的中，强和弱反铁磁相互作用，以及对于后一个交换路径的中性铁磁相互作用）。

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