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Synthesis, Spectral, Structural, Second-Order Nonlinear Optical properties and Theorical Studies on new Organometallic Donor - Acceptor Substituted Nickel(II) and Copper(II) unsymmetrical Schiff-Base complexes
- Source :
- Inorganic Chemistry, Inorganic Chemistry, American Chemical Society, 2010, 49 (6), pp.2750-2764. ⟨10.1021/ic902126a⟩, Inorganic Chemistry, 2010, 49 (6), pp.2750-2764. ⟨10.1021/ic902126a⟩
- Publication Year :
- 2010
- Publisher :
- HAL CCSD, 2010.
-
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(CH(3))N-X-N=CH-(2-O,5-R-C(6)H(3))] (M = Ni (4), Cu (5), X = o-C(6)H(4), R = H; M = Ni (9), X = CH(2)CH(2), R = OH), and their corresponding ionic trinuclear [M{Fc-C(O)CH=C(CH(3))N-X-N=CH-(eta(6)-2-O,5-R-C(6)H(3))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(eta(6)- salicylidene)](+) as a push-pull moiety are reported in this paper (Fc = CpFe(eta(5)-C(5)H(4)); Cp = eta(5)-C(5)H(5); Cp* = eta(5)-C(5)Me(5)). 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(CH(3))N(H)CH(2)CH(2)N=CH-(2,5-(OH)(2)C(6)H(3))] (8) obtained from the Schiff base condensation of 2,5-dihydroxobenzaldehyde with the half-unit precursor, Fc-C(O)CH=C(CH(3))N(H)CH(2)CH(2)NH(2) (2), is reported with its crystal structure showing partial delocalization of the heteroconjugated [O-C-C-C-N] frameworks with a dihedral angle between the respective planes of 60.76 degrees. 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 pi-complexation of the salicylidene ring in the nonlinearity. All the complexes exhibit a second-order nonlinear response increasing with the nuclearity, the hyperpolarizability (beta) value of the trinuclear complex 10 being 1.5 time larger than that of the metalloligand 8 (beta = 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 pi-pi* transitions.
- Subjects :
- Schiff base
010405 organic chemistry
Stereochemistry
Hyperpolarizability
Ionic bonding
Crystal structure
[CHIM.MATE]Chemical Sciences/Material chemistry
Dihedral angle
010402 general chemistry
01 natural sciences
Acceptor
0104 chemical sciences
Inorganic Chemistry
chemistry.chemical_compound
Crystallography
chemistry
Density functional theory
Physical and Theoretical Chemistry
Derivative (chemistry)
Subjects
Details
- Language :
- English
- ISSN :
- 00201669 and 1520510X
- Database :
- OpenAIRE
- Journal :
- Inorganic Chemistry, Inorganic Chemistry, American Chemical Society, 2010, 49 (6), pp.2750-2764. ⟨10.1021/ic902126a⟩, Inorganic Chemistry, 2010, 49 (6), pp.2750-2764. ⟨10.1021/ic902126a⟩
- Accession number :
- edsair.doi.dedup.....33b2e96839bfcc3c3714fb05138f3646