Calculation and electronic description of quadratic hyperpolarizabilities. Toward a molecular understanding of NLO responses in organotransition metal chromophores
01 Dec 1992-Journal of the American Chemical Society (American Chemical Society)-Vol. 114, Iss: 26, pp 10338-10357
TL;DR: In this paper, the use of the computationally efficient, chemically-oriented INDO electronic structure model (ZINDO) in concert with perturbation theory was explored to relate molecular quadratic hyperpolarizabilities to molecular architecture and electronic structure in transition metal chromophores.
Abstract: This contribution explores the use of the computationally efficient, chemically-oriented INDO electronic structure model (ZINDO) in concert with perturbation theory to relate molecular quadratic hyperpolarizabilities to molecular architecture and electronic structure in transition metal chromophores. The ZINDO-derived second-order nonlinear optical responses are found to be in excellent agreement with the experiment for a variety of ferrocenyl and (arene)chromium tricarbonyl derivatives
Citations
More filters
TL;DR: A number of fascinating discoveries are described, including the first demonstration of redox-induced switching of NLO behavior and chromophores which disobey the otherwise universal rule that elongation of polyene systems leads to continual increases in quadratic NLO responses.
Abstract: Organotransition metal complexes have much to offer as nonlinear optical (NLO) chromophores since they allow large hyperpolarizabilities to be combined with various other physical properties in an unparalleled diversity of molecular structures. This Account summarizes our synthetic chemistry driven investigations in the NLO research field, which have focused primarily on complexes of ruthenium, and to some extent iron. A number of fascinating discoveries are described, including the first demonstration of redox-induced switching of NLO behavior and chromophores which disobey the otherwise universal rule that elongation of polyene systems leads to continual increases in quadratic NLO responses.
375 citations
TL;DR: Fractal antenna dendrimers are expected to be promising novel nonlinear optical substances with a controllability of the magnitude and spatial contribution of the third-order NLO properties.
Abstract: This contribution explores the relation between molecular second hyperpolarizabilities (γ) and molecular architecture in phenylacetylene dendrimers using the semiempirical molecular orbital method, that is, INDO/S method. The orientationally averaged γ of a large-size phenylacetylene dendrimer, which is composed of 24 units of phenylacetylenes and is referred to as D25, is found to be about 50 times as large as that of the diphenylacetylene monomer. In contrast, the γs value of D25 is found to be about 6 times as small as that of the para-substituted phenylacetylene oligomer (L25) composed of 24 units of phenylacetylenes. To investigate the structure−property relation in γ for D25 and L25, we examine the spatial contributions of electrons to γ values using γ density analysis. The present analysis reveals that the dominant contributions of electrons to γ of D25 are localized in the linear-leg regions parallel to the applied electric field and the contributions are also well segmented at the meta-connected ...
360 citations
330 citations
TL;DR: In this article, a review of the NLO capabilities of bis(salicylaldiminato) metal Schiff base complexes is presented, where chromophores with enhanced hyperpolarizabilities (β) can be obtained by virtue of the coordinated metal center.
Abstract: Since the mid-1980s, there has been a growth of interest in the search and development of molecular second-order nonlinear optical (NLO) materials that possess various device applications. Beside the most traditional donor-acceptor (“push-pull”) organic chromophores (e.g. the stilbene family), chemists have increasingly extended their field of investigations to newer generations of organic molecules of greater complexity. In recent years, coordination complexes through their unique characteristics such as various redox and magnetic properties, in addition to their great diversity of geometries, have introduced a new dimension to the area. This review attempts to summarize the NLO capabilities of bis(salicylaldiminato)metal Schiff base complexes: (i) chromophores with enhanced hyperpolarizabilities (β) can be obtained by virtue of the coordinated metal center; (ii) the use of chiral substituents allows the engineering of the chromophores into various non-centrosymmetric environments and efficiencies of about 10 times that of urea in second-harmonic generation; (iii) the general trend observed for the high temperature stability in this family of chromophores, while combined with the large β×μ products, makes these systems interesting candidates for their incorporation into poled polymers with high glass transition temperatures (Tg); (iv) the possibility for β modulation induced by magnetic transition is also seen with respect to the concept of molecular switching.
308 citations
TL;DR: In this paper, a review of the structures of polymeric anionic cadmium-thiocyanate coordination solids with cationic crown-ether-metal complexes as spacers, controllers, and templates is presented.
275 citations