Generation of nitric oxide has been a great interest in cell biology as it involves a wide range of physiological functions including the blood pressure control; thus the exploitation of ruthenium chemistry has been motivated in biochemical and clinical points of view. Herein, the structural and electronic properties of ruthenium(II) complexes of 1,4,8,11-tetraazacyclotetradecane containing pyridyl, imidazole and benzimidazole (L1, L2, L3) were analyzed theoretically in the context of how spin multiplicity plays a crucial role influencing the NO release from the LRu-ONO moiety. The results show that β-cleavage of nitrito in the complex motivates the release of NO as it depends highly on total spin multiplicity of metal ion altering significantly the geometrical parameters; particularly, a decrease of bond length of Ru-ONO is highly associated with an increase of RuO-NO bond distance that correlates with the decrease of the Ru-O-NO bond angle ultimately leading to the release of NO; apparently, the bending nature of Ru-O-NO defines its release from the complex. This is consistent with orbital energy (dx2-y2) where the stabilization of axial Ru-O bond in the complex was observed, and proved by molecular orbital studies. In the excitation of the complex (singlet to triplet or singlet to quintet), the NO release has been facilitated, agreeing with the Gibbs free energy data where a lower energy for NO release was obtained compared to other types of excitations. In the calculated electronic spectra, a visible broad band with relatively high intensity for [RuL1ONO]+ was observed, agreeing approximately with reported experimental results.
Keywords: DFT studies; Gibbs free energy; Nitric oxide delivery; Ru-O-NO moiety; Ruthenium complexes; Spin multiplicity.
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