Anion‐Modulated Construction of Two Novel Tetra‐ and Hepta‐Nuclear Ni(II) Salamo‐Type Clusters: Comparison of the DFT Calculations and Weak Interaction Analyses

Abstract

Two novel tetra‐ and hepta‐nuclear Ni(II) salamo‐type clusters, [Ni4(L)2(μ2‐Cl)2(μ3‐OH)2(EtOH)2]⋅4CH2Cl2 (1) and [Ni7(L)3(μ3‐OEt)2(μ3‐OH)6(EtOH)2] (2), were constructed by modulating different anions (Cl− and NO3−). X‐ray crystallographic researches revealed that cluster 1 is a tetranuclear cluster consisting of a symmetric binuclear structure in which chloride ions are involved in coordination. Although cluster 2 consists of seven Ni(II) ions, three deprotonated (L)2− parts, two μ3‐ethoxy groups, six μ3‐OH− anions, and two coordinated ethanol molecules, in which it is quite rare for a large number of water molecules to be deprotonated to participate in the bridging of the cluster due to the alkaline environment. TEM electron scanning displayed the distinct shapes. Comparison of DFT calculations revealed that cluster 2 is less chemically reactive and more kinetically stable, which is in accordance with the analytical results of weak interactions, where the stronger weak interaction forces were presented, the more stable the molecule is. Finally, a comparative analysis of UV–Vis, IR, and fluorescence spectra were carried out.