Highly Dipolar, Optically Nonlinear Adducts of Tetracyano-<i>p</i>-quinodimethane:  Synthesis, Physical Characterization, and Theoretical Aspects

Szablewski, Marek; Thomas, Philip R.; Thornton, Anna; Bloor, D.; Cross, Graham H.; Cole, Jacqueline M.; Howard, Judith A. K.; Malagoli, M.; Meyers, F.; Brédas, Jean‐Luc; Wenseleers, Wim; Goovaerts, E.

doi:10.1021/ja963923w

Cited by 124 publications

(101 citation statements)

References 46 publications

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“…The solvatochromism of high dipole adducts of TCNQ in various dielectric media have been investigated by Szablewski et al [18]. In principle, polar media posses a high reaction field and in this environment a zwitterionic charge separation and stabilisation will occur relative to the gas phase, where the reaction field is zero.…”

Section: Resultsmentioning

confidence: 99%

Orientation and Solvatochromism of Dyes in Liquid Crystals

Pålsson¹,

Szablewski²,

Roberts³

et al. 2003

Molecular Crystals and Liquid Crystals

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Citation for published item: ¦ lssonD vF yF nd zlewskiD wrek nd oertsD eF nd wsutniD eF nd voveD qF hF nd grossD qF rF nd floorD hF nd uyD eF tF nd oolhouseD eF hF nd wsutniD eF nd sudD eF @PHHQA 9yrienttion nd solvtohromism of dyes in liquid rystlsF9D woleulr rystls nd liquid rystlsFD RHP @IAF ppF RQESQF Further information on publisher's website: httpXGGdxFdoiForgGIHFIHVHGURRVITTVS Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. The orientation and solvatochromism of some dye molecules in a liquid crystal have been investigated. Interactions with the host and the structure of the dye molecule affect the macroscopic alignment of dichroic dye molecules in a liquid crystal. It was observed that some dye molecules show a large bathochromic shift of their absorption maxima in the liquid crystal host relative to the situation in isotropic solvents. It is suggested that this is due to the occurrence of a much weaker reaction field in the anisotropic, rigid host. These dye molecules show little or no apparent order in the anisotropic host despite the observation of a reduction in the electro optic switching time when the dye is present. The highest degree of macroscopic alignment was observed for a merocyanine compound, which showed the smallest solvatochromic shift in the liquid crystal host. These results are discussed in terms of the steric, dipolar and hydrogen bond interactions between the guest and the host.

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Section: Resultsmentioning

confidence: 99%

Orientation and Solvatochromism of Dyes in Liquid Crystals

Pålsson¹,

Szablewski²,

Roberts³

et al. 2003

Molecular Crystals and Liquid Crystals

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“…136) similar to those of the analogous compounds. 938,940,942,949,952 Peak B is used in the following analysis. When the overlap of the peaks was significant, the positions of the peaks were determined by line deconvolution into four Gaussian bands.…”

Section: Ionicity Determined By Solvatochromismmentioning

confidence: 99%

“…134g). 938,939,949,[978][979][980] The different conformation originates both from the steric repulsion between the CN1 and 3,3-dimethyl group of the indoline moiety and from the Coulomb attractive interaction between the electronegative CN1 and positively charged N-methyl group. The fluorine atoms are located at the 3,6-position of the 3CNQ moiety, and the fluorine atom closer to the indoline-moiety (F1) is located opposite to the CN1 group, probably owing to their Coulomb repulsion.…”

Section: Molecular and Crystal Structures And Ionicitymentioning

confidence: 99%

“…The structural information has provided valuable aspects in connection with the reaction process, molecular and solid-state properties, and ionicity () of the D-%-A solids. 939,949,[963][964][965] Although the ionicity of the intermolecular CT compounds has been quantitatively discussed in the description of electronic properties 155,164,184 and phase transitions (Peierls, Mott, charge order, neutral-ionic) 178,208,966 of organic (super)-conductors, not so many quantitative experiments concerning functionality vs have been done for the intramolecular CT compounds except for a few cases, [946][947][948] Here, we present an evaluation of the intramolecular CT degree from the solvatochromic shift, and the crystal and molecular structures of D-%-A compounds I n -3CNQ-R (n: alkyl chain C n H 2nþ1 attached to indoline (I) moiety, R: substituents attached to 3CNQ moiety, see Fig. 134) prepared by the Storkenamine type reaction between I and TCNQ derivatives (R-TCNQ), and discuss the relation between the ionicity and the calculated molecular polarizability () and hyperpolarizability ( and ).…”

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Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials

Saito¹,

Yoshida²

2007

Bulletin of the Chemical Society of Japan

370

127

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“…[1][2][3][4][5] On a molecular scale, high levels of charge-transfer and significant transition-state dipole moments are known to lead to good second-order NLO activity in organic materials. The well-known charge-transfer properties of TCNQ adducts, coupled with the fact that two energetically close electronic configurations ͑zwitterionic and quinoidal-see Fig.…”

Section: Introductionmentioning

confidence: 99%

Charge-density study of the nonlinear optical precursor DED-TCNQ at 20 K

et al. 2002

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The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. A charge-density study of the nonlinear-optical ͑NLO͒ precursor ͕4-͓bis͑diethylamino͒-methylium͔ phenyl͖dicyanomethanide ͑DED-TCNQ͒, space group P2 1 /c, aϭ11.174(2) Å; bϭ12.859(2) Å; c ϭ12.486(2) Å; ␤ϭ112.00(1)°, is presented. The results derive from a suitable combination of complementary 20 K x-ray and neutron diffraction data, the latter being important for locating the hydrogen atoms precisely. The compound is one in a series of TCNQ derivatives that exhibit varying degrees of quinoidal and zwitterionic character, these two electronic states being very close energetically. Bond-length-alternation type calculations show that the molecule at 20 K exists in a mixture of the two states, the zwitterionic ground state being dominant ͑63:37% zwitterionic: quinoidal͒. A topological analysis of the bonding density within the benzenoid ring provides for a more direct, alternative method to calculate this ratio which utilizes ellipticity values derived from the charge-density study. Results are identical thus corroborating the validity of the ''strength-length'' relationship implicitly assumed in bond-length-alternation type calculations. The ratio determined corresponds well to the electronic configuration needed to meet the requirements of the general rule for obtaining a maximum value of ␤ ͑a measure of the NLO response on the molecular scale͒ as a function of bond-length alternation. The promise of this class of compounds for nonlinear optics also lies partly in their high molecular dipole moments and so the pseudoatomic charges derived from this study were used to evaluate the nature of the molecular charge transfer in detail and the solid-state dipolar vector moment . Such measurements of are otherwise difficult in the solid state. A value of ͉͉ϭ91ϫ10 Ϫ30 Cm was deduced which compares with liquid and gas phase theoretical calculations of ϭ66.71ϫ10 Ϫ30 Cm and ϭ33.36 ϫ10 Ϫ30 Cm, respectively. This comparison, combined with an analysis of the sense of this vector, show that local crystal-field effects are highly influential in the solid state.

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Highly Dipolar, Optically Nonlinear Adducts of Tetracyano-p-quinodimethane: Synthesis, Physical Characterization, and Theoretical Aspects

Cited by 124 publications

References 46 publications

Orientation and Solvatochromism of Dyes in Liquid Crystals

Orientation and Solvatochromism of Dyes in Liquid Crystals

Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials

Charge-density study of the nonlinear optical precursor DED-TCNQ at 20 K

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