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Second-Order NLO Active Heterotrimetallic Schiff Base Metallopolymer

Abstract : The new ionic heterotrimetallic unsymmetrically-substituted Schiff base complex [Ni₍eta (5)-Cp)Fe(eta (5)-C5H4)-C(=O)CH=C(4-HO-C6H4)NCH2CH2N=CH-(2-O-(eta (6)-C6H4)Ru(eta (5)-Cp*)_][PF6] (3; Cp = C5H5 and Cp* = C-5(CH3)(5)) was prepared in 86% yield by a one-pot procedure by mixing equimolar amounts of 4-hydroxyphenyl functionalized ferrocenylenaminone 1, the organometallic aldehyde [(eta (5)-Cp*)Ru(eta (6)-2-HO-C6H4CHO)][PF6] (2) and nickel(II) acetate tetrahydrate in refluxing ethanol for 2 h. Its corresponding side-chain metallopolymer 4 was synthesized by reacting the organometallic-inorganic hybrid 3 with polyacrylic acid (DP = 25) in DMF at 110 A degrees C for 48 h with an equimolar quantity of N,N'-dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine. The new complex 3 was characterized by FT-IR and multidimensional NMR spectroscopy, elemental analysis and mass spectrometry. Single crystal X-ray diffraction analysis of 3 showed that the ferrocenyl and [(eta (5)-Cp*)Ru](+) units exhibit an anti-conformation and are almost coplanar with the unsymmetrical Schiff base complex fragment, while the 4-HO-C6H4 plane is almost perpendicular. The four-coordinate Ni-II metal ion adopts a square planar geometry, with two nitrogen and two oxygen donor atoms that are mutually trans. Size-Exclusion Chromatography established that metallopolymer 4 is formed of approximately three pendant ionic trimetallic units, while Differential Scanning Calorimetry and Thermal Gravimetric Analysis indicated that 3 and 4 are thermally stable with decomposition temperatures that exceed or border to 250 A degrees C. Harmonic Light Scattering measurements at 1.91 A mu m incident wavelength showed that compounds 3 and 4 exhibit rather high second-order nonlinear responses, with hyperpolarizability beta (1.91) values strongly increasing on passing from the monomeric unit 3 to its metallopolymeric counterpart 4.
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Submitted on : Friday, June 2, 2017 - 3:14:33 PM
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Salvador Celedon, Thierry Roisnel, Isabelle Ledoux-Rak, Jean-René Hamon, David Carrillo, et al.. Second-Order NLO Active Heterotrimetallic Schiff Base Metallopolymer. Journal of Inorganic and Organometallic Polymers and Materials, Springer Verlag (Germany), 2017, 27 (3), pp.795--804. ⟨10.1007/s10904-017-0524-x⟩. ⟨hal-01532180⟩



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