A new dinuclear Ni(II) complex 1, [Ni₂^II(dtbh-PLY)₂], is synthesized from 9-(2-(3,6-di-tert-butyl-2-hydroxybenzylidene)hydrazineyl)-1H-phenalen-1-one, dtbh-PLYH₂ ligand, and structurally characterized by various analytical tools including the single-crystal X-ray diffraction (SCXRD) technique. In the solid state, both Ni(II) metal centers in complex 1 exist in a distorted square planar geometry and display the presence of rare Ni···H–C anagostic interactions to form a one-dimensional (1-D) linear motif in the supramolecular array. Complex 1 is further stabilized in the solid state by π–π-stacking interactions between the highly delocalized phenalenyl rings. The redox features of complex 1 have been analyzed by the cyclic voltammetry (CV) technique in solution as well as in the solid state, revealing the crucial involvement of both the Ni(II) metal centers for undergoing quasi-reversible oxidation reactions on the application of an anodic sweep. A complex 1-modified glassy carbon electrode, GC-1, is employed as an electrocatalyst for oxygen evolution reaction (OER) in 1.0 M KOH, giving an OER onset at 1.45 V, and very low OER overpotential, 300 mV vs the reversible hydrogen electrode (RHE) to reach 10 mA cm^–2 current density. Furthermore, GC-1 displayed fast OER kinetics with a Tafel slope of 40 mV dec^–1, a significantly lower Tafel slope value than those of previously reported molecular Ni(II) catalysts. In situ electrochemical experiments and postoperational UV–vis, Fourier transform infrared (FT-IR), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS), and X-ray photoelectron spectroscopy (XPS) studies were performed to analyze the stability of the molecular nature of complex 1 and to gain reasonable insights into the true OER catalyst.

中文翻译：

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设计基于苯酚基的双核 Ni(II) 配合物：具有两个单 Ni 位点的用于析氧反应 (OER) 的电催化剂


由 9-(2-(3 ,6-二叔丁基-2-羟基苯亚甲基)肼基)-1H-phenalen-1-one, dtbh-PLYH ₂ 配体，并通过各种分析工具（包括单晶 X-）进行结构表征射线衍射（SCXRD）技术。在固态下，配合物 1 中的两个 Ni(II) 金属中心都以扭曲的方形平面几何形状存在，并显示出罕见的 Ni…H-C 抑制相互作用的存在，形成一维 (1-D) 线性图案在超分子阵列中。通过高度离域的苯环之间的 π-π 堆积相互作用，配合物 1 在固态下进一步稳定。通过循环伏安法 (CV) 技术在溶液和固态中分析了配合物 1 的氧化还原特征，揭示了 Ni(II) 金属中心在应用中进行准可逆氧化反应的关键参与阳极扫描。复杂的 1 改性玻碳电极 GC-1 用作 1.0 M KOH 中析氧反应 (OER) 的电催化剂，OER 起始电压为 1.45 V，OER 过电势非常低，相对于可逆氢为 300 mV电极（RHE）达到10 mA cm ^–2 电流密度。此外，GC-1 显示出快速的 OER 动力学，塔菲尔斜率为 40 mV dec ^–1 ，明显低于先前报道的分子 Ni(II) 催化剂的塔菲尔斜率值。 进行原位电化学实验和术后紫外-可见光、傅里叶变换红外 (FT-IR)、扫描电子显微镜-能量色散 X 射线光谱 (SEM-EDS) 和 X 射线光电子能谱 (XPS) 研究来分析配合物 1 分子性质的稳定性并获得对真正的 OER 催化剂的合理见解。