Triphenylcarbinol Derivatives as Molecules for Second-Order Nonlinear Optics

Kelderman, E.; Starmans, W. A. J.; Duynhoven, John van; Verboom, Willem; Engbersen, Johannes F.J.; Reinhoudt, David N.; Derhaeg, L.; Verbiest, Thierry; Clays, Koen; Persoons, André

doi:10.1021/cm00040a013

Cited by 22 publications

(21 citation statements)

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“…67 the ratio of ␤ product for MONS and MONB is equal to 15.3 while a nearly twice lower value was obtained in Ref. 66. We use the latter for comparison because it seems to be more consistent with the other data.…”

Section: Comparison Of the Results: Solvent And Frequency Dependencementioning

confidence: 59%

Applicability of hybrid density functional theory methods to calculation of molecular hyperpolarizability

Suponitsky

Tafur

Masunov

2008

The Journal of Chemical Physics

160

125

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The donor/acceptor (D/A) substituted pi-conjugated organic molecules possess extremely fast nonlinear optical (NLO) response time that is purely electronic in origin. This makes them promising candidates for optoelectronic applications. In the present study, we utilized four hybrid density functionals (B3LYP, B97-2, PBE0, BMK), Hartree-Fock, and second order Moller-Plesset correlation energy correction, truncated at second-order (MP2) methods with different basis sets to estimate molecular first hyperpolarizability (beta) of D/A-substituted benzenes and stilbenes (D=OMe, OH, NMe(2), NH(2); A=NO(2), CN). The results of density functional theory (DFT) calculations are compared to those of MP2 method and to the experimental data. We addressed the following questions: (1) the accurate techniques to compare calculated results to each other and to experiment, (2) the choice of the basis set, (3) the effect of molecular planarity, and (4) the choice of the method. Comparison of the absolute values of hyperpolarizabilities obtained computationally and experimentally is complicated by the ambiguities in conventions and reference values used by different experimental groups. A much more tangible way is to compare the ratios of beta's for two (or more) given molecules of interest that were calculated at the same level of theory and measured at the same laboratory using the same conventions and reference values. Coincidentally, it is the relative hyperpolarizabilities rather than absolute ones that are of importance in the rational molecular design of effective NLO materials. This design includes prediction of the most promising candidates from particular homologous series, which are to be synthesized and used for further investigation. In order to accomplish this goal, semiquantitative level of accuracy is usually sufficient. Augmentation of the basis set with polarization and diffuse functions changes beta by 20%; however, further extension of the basis set does not have significant effect. Thus, we recommend 6-31+G(*) basis set. We also show that the use of planar geometry constraints for the molecules, which can somewhat deviate from planarity in the gas phase, leads to sufficient accuracy (with an error less than 10%) of predicted values. For all the molecules studied, MP2 values are in better agreement with experiment, while DFT hybrid methods overestimate beta values. BMK functional gives the best agreement with experiment, with systematic overestimation close to the factor of 1.4. We propose to use the scaled BMK results for prediction of molecular hyperpolarizability at semiquantitative level of accuracy.

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Section: Comparison Of the Results: Solvent And Frequency Dependencementioning

confidence: 59%

Applicability of hybrid density functional theory methods to calculation of molecular hyperpolarizability

Suponitsky

Tafur

Masunov

2008

The Journal of Chemical Physics

160

125

View full text Add to dashboard Cite

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“…1,[24][25][26][27] We herein describe a different route where push-pull chromophores are gathered in close proximity by covalent linking. Compared to the seminal innovative work by Reinhoudt and coworkers and others, [28][29][30][31][32][33] we focused on strongly dipolar and polarizable chromophores and did not use a large platform (such as cyclodextrins or calixarenes) but very short methylenic (non-conjugated) spacers in order to enhance dipolar interactions between chromophores. Our aim is to take advantage of self-orientation (driven by dipolar repulsion) and mutual polarisation effects (i.e.…”

Section: Introductionmentioning

confidence: 99%

Combined transparency and optical nonlinearity enhancement in flexible covalent multimers by operating through-space interactions between dipolar chromophores

Venkatakrishnan

Pandey

Terenziani

et al. 2014

Phys. Chem. Chem. Phys.

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“…[33] In these cases, the increased response was mainly due to a high degree of alignment of the functionalising chromophores: the hyperpolarizability of the supramolecular structures could be interpreted well by the oriented-gas model, even though, in the case of the polymer, a major contribution to the global dipole moment is made by the main polymer chain. [33] In other examples, the response of multichromophore assemblies shows small [34] or more sizeable deviations [35,36] from additive behavior. These effects were ascribed to dipole-dipole coupling between subchromophores in functionalized cyclodextrins [34] and dendrimers, [36][37][38] and also to possible p-p interactions in functionalized calix [4]arenes.…”

Section: Introductionmentioning

confidence: 99%

“…These effects were ascribed to dipole-dipole coupling between subchromophores in functionalized cyclodextrins [34] and dendrimers, [36][37][38] and also to possible p-p interactions in functionalized calix [4]arenes. [35,39] Another striking example of the role of interchromophore interactions is observed for cyclophane derivatives in which two dipolar push-pull stilbenes that are maintained in a forced relative orientation interact via through-space interactions. [40,41] All these studies point to the importance of structural parameters (geometry, distance, nature of the chromophores) in multichromophore structures and call for further analysis.…”

Section: Introductionmentioning

confidence: 99%

Effects of Dipolar Interactions on Linear and Nonlinear Optical Properties of Multichromophore Assemblies: A Case Study

Terenziani

Mongin

Katan

et al. 2006

Chemistry A European J

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Interchromophore interactions in flexible multidipolar structures for nonlinear optics were addressed by a combined experimental and theoretical study on two series of one-, two-, and three-chromophore systems in which identical push-pull chromophores are assembled through covalent and flexible linkers in close proximity. The photophysical and nonlinear optical properties (quadratic hyperpolarizability) of the multichromophore systems were investigated and compared to those of the monomeric chromophores. Multimers have larger dipole moments than their monomeric analogues, that is, the dipolar subchromophores self-orientate within the multimeric structures. This effect was found to depend on the intersubchromophore distance in a nontrivial manner, which confirms that molecular engineering of such flexible systems is more complex than in completely geometrically controlled systems. Electric-field-induced second-harmonic generation (EFISHG) measurements in solution revealed increased figures of merit as compared to the monomeric analogue. This effect increases with increasing number and polarity of the individual subchromophores in the nanoassembly and increasing spacing between dipolar subchromophores. Experimental results are interpreted by a theoretical model for interacting polar and polarizable chromophores. The properties of multidipolar assemblies are shown to be related to the relative orientation of chromophores, which is imposed by interchromophore interactions. The supramolecular structure is thus a result of self-organization. The proposed theoretical model was also used to predict the properties of multichromophore structures made up of more polar and polarizable push-pull chromophores, and showed that stronger interchromophore interactions can heavily affect the individual optical responses. This suggests new routes for engineering highly NLO responsive multichromophore systems.

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Triphenylcarbinol Derivatives as Molecules for Second-Order Nonlinear Optics

Cited by 22 publications

References 0 publications

Applicability of hybrid density functional theory methods to calculation of molecular hyperpolarizability

Applicability of hybrid density functional theory methods to calculation of molecular hyperpolarizability

Combined transparency and optical nonlinearity enhancement in flexible covalent multimers by operating through-space interactions between dipolar chromophores

Effects of Dipolar Interactions on Linear and Nonlinear Optical Properties of Multichromophore Assemblies: A Case Study

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