Structural, Electronic, Thermodynamic and Nonlinear Optical Properties of a Novel Ce(III) Complex with Ferrocenyl Dithiophosphonate


AYDIN A., DEDE B.

Acta Physica Polonica A, cilt.148, sa.1, ss.3-11, 2025 (SCI-Expanded, Scopus)

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 148 Sayı: 1
  • Basım Tarihi: 2025
  • Doi Numarası: 10.12693/aphyspola.148.3
  • Dergi Adı: Acta Physica Polonica A
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Chemical Abstracts Core, Compendex, INSPEC
  • Sayfa Sayıları: ss.3-11
  • Anahtar Kelimeler: cerium complex, density functional theory (DFT), quantum mechanical calculation, topics: dithiophosphonate
  • Süleyman Demirel Üniversitesi Adresli: Evet

Özet

In this study, a novel cerium(III) complex featuring a ferrocenyl dithiophosphonate ligand was synthesized and comprehensively characterized using a range of spectroscopic and analytical techniques. The synthetic route involves the esteri cation of 2,4-diferrocenyl-1,3-dithiadiphosphetane disul de (ferrocenyl Lawesson's reagent) with isopropyl alcohol, followed by conversion to its ammonium salt and subsequent complexation with Ce(NO3)3 · 6H2O in tetrahydrofuran. The structure of the complex was elucidated using Fourier transform infrared spectroscopy, 1H- and 31P-nuclear magnetic resonance spectroscopy, thermal analysis, and elemental analysis. Spectroscopic results indicated successful coordination of Ce(III) through the dithiophosphonate moieties. Quantum mechanical calculations at the density functional theory/Becke, 3-parameter, Lee-Yang-Parr level provided insight into the geometric, electronic, and thermodynamic properties of the Ce(III) complex. The total density of states and frontier molecular orbital analyses revealed an energy gap of ∆E = 9.042 eV of the singly occupied-lowest unoccupied molecular orbitals, indicating high electronic stability. Theoretical calculations highlighted the signi cant nonlinear optical properties of a Ce(III) complex, demonstrating its potential for enhanced nonlinear optical performance due to the synergistic effects of the ferrocenyl dithiophosphonate ligand and Ce(III) ion. Additionally, thermodynamic parameters such as zero-point energy, entropy, and heat capacity were calculated, con rming the structural stability and potential functional applications of the synthesized Ce(III) complex in photophysical or catalytic systems.