Synthesis, spectral, structural, second-order nonlinear optical properties and theoretical studies on new organometallic donor-acceptor substituted nickel(ii) and copper(ii) unsymmetrical schiff-base complexes

Alexander Trujillo, Mauricio Fuentealba, David Carrillo, Carolina Manzur, Isabelle Ledoux-Rak, Jean René Hamon, Jean Yves Saillard

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Abstract

The synthesis, spectroscopic and structural characterization, linear and nonlinear optical properties, as well as the electrochemical behavior of a series of robust neutral binuclear M[Fc-C(O)CH=C(CH3)N-X-N=CH-(2-O,5- R-C6H3)] (M = Ni (4), Cu (5), X = o-C6H 4, R = H; M = Ni (9), X = CH2CH2, R = OH), and their corresponding ionic trinuclear [M{Fc-C(O)CH=C(CH3)N-X-N=CH- (η6-2-O,5-R-C6H3)RuCp*}][PF 6] (6, 7, 10), M[ONNO]-type unsymmetrical Salophen and salen complexes featuring ferrocenyl (Fc) donor and the mixed sandwich acceptor [Cp*Ru(η6-salicylidene)]+ as a push-pull moiety are reported in this paper (Fc = CpFe(η5-C5H 4); Cp = η5-C5H5; Cp* = η5-C5Me5). The single-crystal X-ray structure of the bimetallic iron-nickel derivative 4 indicates a bowed structure of the unsymmetrical Schiff base skeleton. The Ni(II) ion is tetracoordinated in a square planar environment, with two nitrogen atoms and two oxygen atoms as donors. The new metalloligand [Fc-C(O)CH=C(CH3)N-(H)CH 2CH2N=CH-(2,5-(OH)2C6H3)] (8) obtained from the Schiff base condensation of 2,5-dihydroxobenzaldehyde with the half-unit precursor, Fc-C(O)CH=C(CH3)N(H)CH 2CH2NH2 (2), is reported with its crystal structure showing partial derealization of the heteroconjugated [O-C-C-C-N] frameworks with a dihedral angle between the respective planes of 60.76°. Second order nonlinear optical (NLO) measurements were achieved using the Harmonic Light Scattering technique to probe the role of the M[ONNO] chromophores and of the π-complexation of the salicylidene ring in the nonlinearity. All the complexes exhibit a second-order nonlinear response increasing with the nuclearity, the hyperpolarizability (β) value of the trinuclear complex 10 being 1.5 time larger than that of the metalloligand 8 (β = 155 x 10-30 esu). A rationalization of the structural, electronic, and redox properties of the title compounds is provided, based on a theoretical investigation at the density functional theory (DFT) level. Their UV-visible spectra has been assigned with the help of time-dependent (TD) DFT calculations. They are dominated by LMCT, MLCT, and π - π* transitions.

Original languageEnglish
Pages (from-to)2750-2764
Number of pages15
JournalInorganic Chemistry
Volume49
Issue number6
DOIs
StatePublished - 15 Mar 2010
Externally publishedYes

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