In total, 13 ligands R-salen (N,N’-bis(5-R-salicylidene)ethylenediamine (where R = MeO, Me, OH, H, Cl, Br, NO₂) and R-salphen (N,N’-bis(5-R-salicylidene)-1,2-phenylenediamine (where R = MeO, Me, OH, H, Cl, Br) and their 13 nickel complexes NiRsalen and NiRsalphen were synthesized and characterized using IR (infrared) spectroscopy, mass spectrometry, elemental analysis, magnetic susceptibility, NMR (nuclear magnetic resonance), UV-vis (ultraviolet-visible) spectroscopy, cyclic voltammetry, and X-ray crystal diffraction. Previous studies have shown that all complexes have presented a square planar geometry in a solid state and as a solution (DMSO). In electrochemical studies, it was observed that in N/N aliphatic bridge complexes, the Ni^II underwent two redox reactions, which were quasi-reversible process, and the half-wave potential followed a trend depending on the ligand substituent in the 5,5’-R position. The electron-donor substituent—as -OH, and -CH₃ decreased the E_1/2 potential—favored the reductor ability of nickel. The crystals of the complexes NiMesalen, NiMeOsalen, NiMeOsalphen, and Nisalphen were obtained. It was shown that the crystal packaging corresponded to monoclinic systems in the first three cases, as well as the triclinic for Nisalphen. The Hirshfeld surface analysis showed that the packaging was favored by H∙∙∙H and C∙∙∙H/H∙∙∙C interactions, and C-H∙∙∙O hydrogen bridges when the substituent was -MeO and π-stacking was added to an aromatic bridge. Replacing the N/N bridge with an aromatic ring decreased distortion in square-planar geometry where the angles O-Ni-N formed a perfect square-planar.

中文翻译：

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N / N桥类型及其取代基对席夫碱（Salen / Salphen）Niii配合物的化学和晶体学性质的影响

总共有13个配体R- Salen（N，N'-双（5-R-水杨基）亚乙基二胺（其中R = MeO，Me，OH，H，Cl，Br，NO ₂）和R-赛尔芬（N，N -双（5-R-水杨基）-1,2-苯二胺（其中R = MeO，Me，OH，H，Cl，Br）及其13个镍配合物NiR Salen和NiR Salphen合成并使用IR（红外）光谱，质谱，元素分析，磁化率，NMR（核磁共振），UV-vis（紫外-可见）光谱，循环伏安法和X射线晶体衍射进行表征。先前的研究表明，所有配合物在固态和溶液（DMSO）中均呈方形平面几何形状。在电化学研究中，观察到在N / N脂族桥络合物中，Ni ^II经历了两次氧化还原反应，这是准可逆的过程，并且半波电势遵循取决于5,5中配体取代基的趋势。 '-R位置。电子给体取代基-OH和-CH ₃降低E _1/2电位—有利于镍的还原能力。络合物NIME的晶体沙仑，NiMeO出售N，NiMeOs尔芬，和Ni salphen获得。结果表明，在前三种情况下，晶体包装与单斜晶系相对应，而镍斜线晶体与三斜晶系相对应。Hirshfeld表面分析表明，包装因H∙∙∙H和C∙∙∙H / H∙∙∙C相互作用而受到青睐，并且当取代基为-MeO和π堆积时，CH∙∙∙O氢桥到芳香桥。用芳环取代N / N桥可减少角为O-Ni-N形成理想的正方形平面的正方形平面几何形状的畸变。