(Dicyanomethylene)pyran Derivatives with C2v Symmetry:  An Unusual Class of Nonlinear Optical Chromophores

Moylan, Christopher R.; Ermer, Susan; Lovejoy, Steven M.; McComb, I-Heng; Leung, Doris S.; Wortmann, Rüdiger; Krdmer, Peter; Twieg, Robert J.

doi:10.1021/ja962673g

Cited by 187 publications

(107 citation statements)

References 23 publications

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“…It was noted that ethylenedithio substitution, i.e., compound 53, blue-shifts this band to l max = 594 nm, while increasing the mb(0) value, which may be beneficial in controlling the well-known transparency±non-linear efficiency trade-off in NLO materials. [13,67] It is clear from these initial studies that TTF is emerging as a new pdonor in the field of NLO materials. Issues of thermal stability and processability need to be addressed to establish the extent to which TTF-based NLO materials may be of practical value.…”

Section: Mesomerically Conjugated Carbonyl Thiocarbonyl Ester and mentioning

confidence: 99%

Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Bryce

1999

Adv. Mater.

334

144

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Although tetrathiafulvalene (TTF) and its derivatives have been extensively studied for more than 25 years as p-electron donors in intermolecular charge-transfer materials, the intriguing potential of TTF as a donor in an intramolecular sense has only recently been developed. Many versatile, functionalized TTF building blocks are now readily available, and this article will review a range of compounds in which TTF is covalently linked to an electron acceptor moiety by a variety of linking units, sometimes giving rise to an intramolecular charge-transfer (ICT) interaction, which is most frequently manifested in the optical and electrochemical properties. In this context, acceptor subunits include: tetracyano-p-quinodimethane, quinones, electrondeficient aryl groups, pyridinium and bipyridinium units, fullerenes, phthalocyanines, and mesomerically conjugated carbonyl, thiocarbonyl, ester, and related groups. This work paves the way for more systematic and detailed studies of TTF±spacer±A molecules (where A is an acceptor) in which there is increased control of the structural, electronic, optical, and magnetic properties arising from ICT interactions in the ground state, or in the excited state.

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Section: Mesomerically Conjugated Carbonyl Thiocarbonyl Ester and mentioning

confidence: 99%

Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Bryce

1999

Adv. Mater.

334

144

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“…Finally, the 2/3 substitution rate leads to a supramolecular L-shape lateral packing of the chromophores. [48][49] Geometry optimizations carried out at the MM/OPLS-AA level of approximation show that the variation of the radial displacements in the 3m, 3m+1, and 3m+2 series are smaller than in the case of the nonsubstituted helices. Indeed, by going from 3 to 27 units, the radial displacement goes from 1858 to 1098, with a periodicity of about 38 units.…”

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confidence: 97%

Theoretical Investigation of the Second‐Order Nonlinear Optical Properties of Helical Pyridine–Pyrimidine Oligomers

Botek

Castet

Champagne

2006

Chemistry A European J

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The structure and second-order nonlinear optical properties of a series of helical pyridine-pyrimidine oligomers recently synthesized by Barboiu and Lehn have been investigated theoretically by combining molecular mechanics and quantum chemistry approaches. In the absence of substituents, the hyper-Rayleigh scattering response (betaHRS) and the projection of the first hyperpolarizability on the dipole moment (beta||) exhibit periodic variations with chain length, but these nonlinear optical responses remain small. The first hyperpolarizabilities can, however, be enhanced by adding substituents. The greatest enhancement is obtained by substituting the pyrimidine groups by donor groups. Moreover, regular distributions of the donor groups around the helices enable the design of supramolecular structures exhibiting dipolar, octupolar or Lambda-shaped nonlinear optical characters, evident from the values of the depolarization ratios in hyper-Rayleigh scattering. Therefore this theoretical investigation demonstrates the potential of helical structures for the organization of chromophores in such a way that they exhibit large and specific second-order nonlinear optical responses.

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“…Semiempirical calculations for several Λ-shaped molecules indicate that some molecules of this type indeed do have quite strongly absorbing low-lying states with the appropriate symmetry. 15 In addition, Eq. (6) indicates that the molecular r esponse will be enhanced in the anomalous dispersion regime, e.g.…”

Section: 2mentioning

confidence: 99%

Optimization of the nonlinear optical response in chiral media

et al. 2001

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This paper describes the development and optimization of chiral, non-polar media with large second-order nonlinear optical responses. We employ molecular engineering, quantum-mechanical sum-over-states theory, and measurements of molecular hyperpolarizability by means of Kleinman-disallowed hyper-Rayleigh scattering in order to understand molecular properties. Then we analyze the appropriate arrangement of the chromophores that produce an optimum axial nonlinear optical medium. Chromophores with large Kleinman disallowed traceless symmetric second rank tensor hyper-polarizabilities β can be aligned so as to result in large susceptibilities, χ (2) , in structures that lack polar order. We found that L-shaped chromophores with C 2v or similar symmetry are good candidates for these materials as they can exhibit large second-rank components of the hyperpolarizability tensor. A wide variety of techniques can be used to fabricate bulk materials belonging to the chiral non-polar symmetry groups, D ∞ and D 2 . The microscopic chromophore alignment schemes that optimize the NLO response in such materials are deduced from general symmetry consideration for both molecules and bulk.

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(Dicyanomethylene)pyran Derivatives with C₂_v Symmetry: An Unusual Class of Nonlinear Optical Chromophores

Cited by 187 publications

References 23 publications

Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Theoretical Investigation of the Second‐Order Nonlinear Optical Properties of Helical Pyridine–Pyrimidine Oligomers

Optimization of the nonlinear optical response in chiral media

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