Side‐Chain Metallopolymers Containing Second‐Order NLO‐Active Bimetallic NiII and PdII Schiff‐Base Complexes: Syntheses, Structures, Electrochemical and Computational Studies. Issue 18 (28th April 2016)

• Record Type: Journal Article
• Authors: Celedón, Salvador; Fuentealba, Mauricio; Roisnel, Thierry; Ledoux‐Rak, Isabelle; Hamon, Jean‐René; Carrillo, David; Manzur, Carolina
• Is Part Of: European journal of inorganic chemistry. Issue 18(2016)
• Page Start: 3012
• Page End: 3023
• Publication Date: 2016-04-28
• Subjects: Nickel -- Palladium -- Schiff bases -- Ligand design -- N2O2 ligand -- Polymers -- Metallopolymers -- Nonlinear optics; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201600236
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Unsymmetric Schiff‐base metalloligand precursor2 is synthesized by condensation of phenol‐functionalized ferrocenylenaminone1 with 2‐hydroxy‐5‐nitrobenzaldehyde. Heterobimetallic complexes3 and4 result from the N2 O2 ‐tetradentate coordination of Ni II and Pd II metal ions with the doubly deprotonated form of2, respectively. Linking3 and4 to polyacrylic acid through an esterification reaction leads to the formation of the corresponding side‐chain metallopolymers5 and6 . The new compounds were fully characterized (IR, UV/Vis, NMR, MS, CV, SEC) and structures of2 –4 unequivocally determined by single‐crystal X‐ray diffraction techniques. Decomposition temperatures higher than 250 °C were found by DSC and TGA techniques for3 –6 . Harmonic light scattering measurements showed that compounds2 –5 exhibit rather high second‐order nonlinear responses, between 200 × 10 –30 and 970 × 10 –30 esu, with the hyperpolarizability β 1.91 value increasing significantly on passing from Ni II complex3 to its respective metallopolymer5 . The structural and electronic properties of2 –4 are analyzed by DFT and TD‐DFT calculations. Abstract : The redox active heterobimetallic subunits and their derived side‐chain metallopolymer Schiff‐base compounds exhibit good thermal stability and high second‐order NLO responses. The electronic structure of the bimetallic species is analyzed by DFT and TD‐DFT calculations.