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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Push-pull unsymmetrical substitution in nickel(II) complexes with tetradentate N2O2 Schiff base ligands: synthesis, structures and linear-nonlinear optical studies
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Push-pull unsymmetrical substitution in nickel(II) complexes with tetradentate N2O2 Schiff base ligands: synthesis, structures and linear-nonlinear optical studies

机译：镍（II）配合物中的推挽不对称取代与四ententateN2O2席夫碱配体：合成，结构和线性非线性光学研究

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摘要

New push-pull (A-D) nickel(II) compounds of general formula [Ni(5-A-5'-D-saltn)] (3a-3l) with unsymmetrically-substituted N2O2 tetradentate Schiff base ligands are reported here. The ligands 5-A-5'-D-saltn(2-) (H(2)saltn = N,N'-bis(salicylidene) diaminopropane) possess differently-substituted salicylaldehyde ((A/D)sal) moieties condensed to 1,3-diaminopropane (tn), and carry either an electron acceptor (A = H, Br, or NO2) or donor (D = H, Me, or OMe) group in the para position with respect to the coordinated phenoxido oxygen atoms. These compounds could be obtained by template synthesis involving derivatives [Ni(Gsal)(2)(H2O)(2)], 1a-e (G = NO2, Br, H, Me and OMe, respectively) and [Ni(L-G)2], 2a-d (L-G-= (E)2-(( 3-aminopropylimino) methyl)-4-G-phenolate, G = NO2, Br, H and Me, respectively). Scrambling of the ligands and condensation to compounds 3 was suitably achieved by refluxing compounds 1 and 2 that carry the G groups suitable for the desired final A-D combination. Dinuclear intermediates [Ni-2(mu-L-G)2((')G'sal)(2)] (4a, b, e, f, g) were also detected and isolated. The single-crystal X-ray diffraction structures of [Ni(5'-OMe-saltn)]center dot CHCl3 (3c center dot CHCl3), [Ni(5-Br-5'-OMe-saltn)]center dot EtOH (3g center dot EtOH) and [Ni(5-NO2-saltn)] (3j) show different degrees of distortion around the central core, leading to saddle-like (3c), planar (3g) and step-like (3j) molecular conformations. DFT geometrical optimization of the compounds showed that, for isolated molecules, the saddle-like conformation is slightly more stable with respect to the other conformations. UV-visible absorption spectra showed structured absorption profiles at about 320-440 nm, whose intensity was amplified by the presence of the nitro group, and this was assigned to a convolution of one metal-to-ligand charge transfer and two intra-ligand charge transfer transitions by TDDFT computations. Surprisingly, UV-visible spectra of the derivatives with Br were comparable to the de
机译：新推挽（A-d）镍（II）通式[镍（5-A-5'-d-saltn）]（3A-3L）与不对称取代的四齿N2O2席夫碱配体这里报告。配体5-A-5'-d-saltn（2-）（H（2）saltn = N，N'-双（亚水杨基）二氨基丙烷）具有不同取代的水杨醛（（A / d）SAL）部分冷凝至1,3-二氨基丙烷（TN），和进位或者电子受体（A = H，Br或NO 2）或施主（d = H，Me或OME）在对位组相对于协调phenoxido氧原子。这些化合物可以通过模板合成涉及衍生物来获得[镍（GSAL）（2）（H 2 O）（2）]，1A-E（分别为G = NO 2，BR，H，我和OME，）和[镍（LG） 2]，图2a-d（LG- =（E）2 - （（3- aminopropylimino）甲基）-4-G-苯酚，G = NO 2，BR，分别H和Me）。配体和缩合的化合物3的加扰被合适地通过回流携带适合于期望的最终A-d的组合的G基团的化合物1和2来实现的。双核中间体[Ni基2（MU-L-G）2（（'）G'sal）（2）]（4A，B，E，F，G）也进行检测和隔离。的单晶X射线衍射结构[镍（5'-OME-saltn）]中心点的CHCl 3（3C中心点的CHCl 3），[镍（5-溴-5'- OME-saltn）]中心点的EtOH（ 3克中心点乙醇）和[镍（5-NO2-saltn）]（3J）表现出不同程度的围绕中央芯失真，导致鞍状（3c）中，平面的（3G）和阶梯状（3J）分子构象。化合物的DFT几何优化显示，对于分离的分子，所述鞍状构象是稍微更稳定相对于其他构象。 UV-可见光吸收谱显示在约320-440纳米结构化的吸收曲线，其强度由硝基的存在下扩增，将其分配给一个金属到配体的电荷转移和两种帧内配体的电荷的卷积通过TDDFT计算转移的过渡。令人惊讶地，用溴衍生物的紫外 - 可见光谱是可比到解

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