Second-Order NLO Active Heterotrimetallic Schiff Base Metallopolymer

Abstract

The new ionic heterotrimetallic unsymmetrically-substituted Schiff base complex [Ni{(η 5-Cp)Fe(η 5-C5H4)-C(=O)CH=C(4-HO-C6H4)NCH2CH2N=CH-(2-O-(η 6-C6H4)Ru(η 5-Cp*)}][PF6] (3; Cp = C5H5 and Cp* = C5(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 [(η 5-Cp*)Ru(η 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 °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 [(η 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 NiII 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 °C. Harmonic Light Scattering measurements at 1.91 µm incident wavelength showed that compounds 3 and 4 exhibit rather high second-order nonlinear responses, with hyperpolarizability β 1.91 values strongly increasing on passing from the monomeric unit 3 to its metallopolymeric counterpart 4.