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

详细信息    查看全文

• 作者：Salvador Celedó ; n ; Mauricio Fuentealba ; Thierry Roisnel ; Isabelle Ledoux-Rak ; Jean-René ; Hamon ; David Carrillo and Carolina Manzur
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：June 2016
• 年：2016
• 卷：2016
• 期：18
• 页码：3012-3023
• 全文大小：1645K
• ISSN：1099-0682c

文摘

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 Ni^II and Pd^II metal 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^–30 and 970 × 10^–30 esu, with the hyperpolarizability β_1.91 value increasing significantly on passing from Ni^II complex 3 to its respective metallopolymer 5. The structural and electronic properties of 2–4 are analyzed by DFT and TD-DFT calculations.