Side-Chain Metallopolymers Containing Second-Order NLO-Active Bimetallic NiII and PdII Schiff-Base Complexes: Syntheses, Structures, Electrochemical and Computational Studies

Salvador Celedón, MAURICIO DANIEL FUENTEALBA CARRASCO, Thierry Roisnel, Isabelle Ledoux-Rak, Jean René Hamon, David Carrillo, Carolina Manzur

Research output: Contribution to journalArticlepeer-review

15 Scopus citations

Abstract

Unsymmetric Schiff-base metalloligand precursor 2 is synthesized by condensation of phenol-functionalized ferrocenylenaminone 1 with 2-hydroxy-5-nitrobenzaldehyde. Heterobimetallic complexes 3 and 4 result from the N2O2-tetradentate coordination of NiIIand PdIImetal ions with the doubly deprotonated form of 2, respectively. Linking 3 and 4 to polyacrylic acid through an esterification reaction leads to the formation of the corresponding side-chain metallopolymers 5 and 6. The new compounds were fully characterized (IR, UV/Vis, NMR, MS, CV, SEC) and structures of 2–4 unequivocally determined by single-crystal X-ray diffraction techniques. Decomposition temperatures higher than 250 °C were found by DSC and TGA techniques for 3–6. Harmonic light scattering measurements showed that compounds 2–5 exhibit rather high second-order nonlinear responses, between 200 × 10–30and 970 × 10–30esu, with the hyperpolarizability β1.91value increasing significantly on passing from NiIIcomplex 3 to its respective metallopolymer 5. The structural and electronic properties of 2–4 are analyzed by DFT and TD-DFT calculations.

Original languageEnglish
Pages (from-to)3012-3023
Number of pages12
JournalEuropean Journal of Inorganic Chemistry
Volume2016
Issue number18
DOIs
StatePublished - 1 Jan 2016

Keywords

  • Ligand design
  • Metallopolymers
  • NOligand
  • Nickel
  • Nonlinear optics
  • Palladium
  • Polymers
  • Schiff bases

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