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Abstract <p>A comprehensive characterization of PMDP and its ruthenium(II) complex, Ru(II)bpyPMDP, was undertaken using various spectroscopic techniques. Mass spectrometry revealed molecular ion peaks at <i>m</i>/<i>z</i> = 819 and 990 for PMDP and Ru(II)bpyPMDP, respectively, corroborating their proposed molecular structures. Elemental analysis further validated the composition of both compounds, with experimental values exhibiting good correlation with calculated values. FT-IR spectroscopy confirmed the structural characteristics of PMDP and its Ru(II) complex, indicating that PMDP acts as a bidentate ligand via two azomethine nitrogen atoms. <sup>1</sup>H NMR spectroscopy revealed significant downfield shifts in the azomethine proton resonance, confirming the coordination of PMDP to the ruthenium ion. The electronic absorption spectra of Ru(II)bpyPMDP in methanol exhibited intense absorptions attributed to π–π*/LLCT, <i>n</i>–π*, and MLCT transitions, indicating an octahedral environment around the ruthenium(II) center. The emission spectrum of Ru(II)bpyPMDP in methanol displayed a broad peak at 529−607 nm, indicating a strong luminescent property. Density functional theory (DFT) calculations revealed non-planar optimized structures for PMDP and its complexes. The HOMO of PMDP was found to be localized on iodine, oxygen, and aldehyde benzene ring atoms, while the LUMO was mainly localized on azomethine nitrogen and diamino benzene ring atoms, with a calculated HOMO-LUMO energy gap of 1.4474 eV. The HOMO and LUMO distributions of Ru(II)bpyPMDP were analyzed, revealing a small HOMO-LUMO energy gap (2.5538–3.9279 eV) that indicates high chemical reactivity and polarizability. Mulliken atomic charge calculations for PMDP and its Ru(II) complexes revealed that hydrogen atoms have positive charges, while oxygen, nitrogen, and iodine atoms have negative charges, indicating their roles as donor atoms. The 3D molecular electrostatic potential (MEP) plots of PMDP and its Ru(II) complexes revealed regions of high electron density (red) and low electron density (blue), indicating electrophilic and nucleophilic sites, respectively.</p>

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Design, Synthesis, and Computational Analysis of Ruthenium(II) Complexes with o-Phenylenediamine (3,5,Diiodosalicylaldehyde) Ligand: Insights into Their Stability and Reactivity

  • 期刊论文

  • 发表日期：

    2025年6月1日

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  • S. L. Sathya Saibaba,
  • K. Swarnalatha,
  • S. Kamalesu,
  • S. C. Vella Durai

摘要

Abstract

A comprehensive characterization of PMDP and its ruthenium(II) complex, Ru(II)bpyPMDP, was undertaken using various spectroscopic techniques. Mass spectrometry revealed molecular ion peaks at m/z = 819 and 990 for PMDP and Ru(II)bpyPMDP, respectively, corroborating their proposed molecular structures. Elemental analysis further validated the composition of both compounds, with experimental values exhibiting good correlation with calculated values. FT-IR spectroscopy confirmed the structural characteristics of PMDP and its Ru(II) complex, indicating that PMDP acts as a bidentate ligand via two azomethine nitrogen atoms. 1H NMR spectroscopy revealed significant downfield shifts in the azomethine proton resonance, confirming the coordination of PMDP to the ruthenium ion. The electronic absorption spectra of Ru(II)bpyPMDP in methanol exhibited intense absorptions attributed to π–π*/LLCT, n–π*, and MLCT transitions, indicating an octahedral environment around the ruthenium(II) center. The emission spectrum of Ru(II)bpyPMDP in methanol displayed a broad peak at 529−607 nm, indicating a strong luminescent property. Density functional theory (DFT) calculations revealed non-planar optimized structures for PMDP and its complexes. The HOMO of PMDP was found to be localized on iodine, oxygen, and aldehyde benzene ring atoms, while the LUMO was mainly localized on azomethine nitrogen and diamino benzene ring atoms, with a calculated HOMO-LUMO energy gap of 1.4474 eV. The HOMO and LUMO distributions of Ru(II)bpyPMDP were analyzed, revealing a small HOMO-LUMO energy gap (2.5538–3.9279 eV) that indicates high chemical reactivity and polarizability. Mulliken atomic charge calculations for PMDP and its Ru(II) complexes revealed that hydrogen atoms have positive charges, while oxygen, nitrogen, and iodine atoms have negative charges, indicating their roles as donor atoms. The 3D molecular electrostatic potential (MEP) plots of PMDP and its Ru(II) complexes revealed regions of high electron density (red) and low electron density (blue), indicating electrophilic and nucleophilic sites, respectively.