Three polar derivatives of<i>N</i>-ethylcarbazole: materials for optical applications

Нестеров, В. Н.; Montoya, Nicole G.; Antipin, M. Yu.; Sanghadasa, Mohan; Clark, Ronald D.; Timofeeva, Tatiana V.

doi:10.1107/s0108270101020170

Cited by 11 publications

(10 citation statements)

References 11 publications

(9 reference statements)

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“…Moreover, Figure 1 reveals that the C11=C12 double bond has Z geometry, and that there is a large twist between the thiazole and the phenyl rings (dihedral angle N2-C13-C18-C23: 62.68). The steric hindrance between the substituent at 5-position of the thiazole ring and the phenyl group might be the origin of such a large dihedral angle, because in 5-unsubstituted 4-phenylthiazoles the rings are essentially coplanar, [26] whereas this is not the case for their 5-substituted analogues. [27] Notably, the packing in the crystal is polar (in keeping with the space group, P2 1 ), meaning that this material will show bulk NLO activity.…”

Section: Resultsmentioning

confidence: 97%

Aromatic/Proaromatic Donors in 2‐Dicyanomethylenethiazole Merocyanines: From Neutral to Strongly Zwitterionic Nonlinear Optical Chromophores

Andreu

Galán

Orduna

et al. 2010

Chemistry A European J

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Push-pull compounds, in which a proaromatic electron donor is conjugated to a 2-dicyanomethylenethiazole acceptor, have been prepared, and their properties compared to those of model compounds featuring an aromatic donor. A combined experimental (X-ray diffraction, (1) H NMR, IR, Raman, UV/Vis, nonlinear optical (NLO) measurements) and theoretical study reveals that structural and solvent effects determine the ground-state polarisation of these merocyanines: whereas 4H-pyran-4-ylidene- and 4-pyridylidene-containing compounds are zwitterionic and 1,3-dithiol-2-ylidene derivatives are close to the cyanine limit, anilino-derived merocyanines are essentially neutral. This very large range of intramolecular charge transfer (ICT) gives rise to efficient second-order NLO chromophores with μβ values ranging from strongly negative to strongly positive. In particular, pyranylidene derivatives are unusual in that they show an increase in the degree of ICT on lengthening the π-spacer, a feature that lies behind the very large negative μβ values they display. The linking of the formally quinoidal 2-dicyanomethylenethiazole moiety to proaromatic donors seems a promising approach towards the optimisation of zwitterionic NLO chromophores.

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Section: Resultsmentioning

confidence: 97%

Aromatic/Proaromatic Donors in 2‐Dicyanomethylenethiazole Merocyanines: From Neutral to Strongly Zwitterionic Nonlinear Optical Chromophores

Andreu

Galán

Orduna

et al. 2010

Chemistry A European J

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“…We noted earlier that for the series of compounds we have studied 26,27 the same effect of a rise of the melting points for analogous compounds with and without intermolecular hydrogen bonds might be even higher (more than 70°C). In particular, for two dicyanoethenyl derivatives, namely, 1,1-dicyano-2-(4-hydroxyphenyl)-ethene (DHE) and 1,1-dicyano-2-(4-methoxyphenyl)-ethene (DME) 26 (scheme below), the melting point of DHE which forms hydrogen bonds in a crystal is equal to 188-189°C, while for DME it is much lower, at 114-115°C.…”

Section: Introductionmentioning

confidence: 91%

Thermally Stable Imines as New Potential Nonlinear Optical Materials

Nesterov

Antipin

Нестеров

et al. 2004

Crystal Growth & Design

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In the search for new thermostable acentric nonlinear optical (NLO) crystalline materials, several polar imine derivatives with the general structure D-π-A(D′) were synthesized and studied. Introduction of the amino group (D′) into the acceptor moiety of these molecules was supposed to bring hydrogen bonds into the crystal structures, and so to elevate their melting points and to assist acentric molecular packings. Ten compounds of this type have been prepared, and for six of them single crystals have been grown and characterized by X-ray diffraction analysis. High melting points were found for all synthesized compounds. It was found that four compounds have acentric crystal structures. Analysis of the crystal packing and hydrogen bonding in the compounds studied has been carried out along with quantum calculations of the molecular NLO responses. This allowed an understanding of the thermal stability of the compounds studied and some of their NLO characteristics.

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“…The present investigation is a continuation of a project that includes syntheses and structural studies of polar conjugated organic compounds that crystallize in non-centrosymmetric space groups (Antipin et al, 1998;Nesterov et al, 1998Nesterov et al, , 2000Nesterov, Antipin, Nesterov, Moore et al, 2004;Nesterov, Antipin, Nesterov, Penn et al, 2004). These compounds may ®nd applications in non-linear optical materials (Zyss, 1994;Kuzyk & Dirk, 1998) and in the syntheses of heterocyclic compounds (Brunskill et al, 1984;Nesterov et al, 2002). Moreover, related compounds have found applications as potential antitumor drugs (Hutchinson et al, 2001;Thacher et al, 2001;Wermuth, 2004).…”

Section: Commentmentioning

confidence: 96%

Polymorphism and solvolysis of 2-cyano-3-[4-(N,N-diethylamino)phenyl]prop-2-enethioamide

Нестеров

Nesterov

2004

Acta Crystallogr C

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Two new polymorph forms, (Ia) and (Ib), of the title compound, C(14)H(17)N(3)S, and its solvate with acetonitrile, C(14)H(17)N(3)S.0.25C(2)H(3)N, (Ic), have been investigated. Crystals of the two polymorphs were grown from different solvents, viz. ethanol and N,N-dimethylformamide, respectively. The polymorphs have different orientations of the thioamide group relative to the CN substituent, with s-cis and s-trans geometry of the C=C-C=S diene fragment, respectively. Compound (Ic) contains two independent molecules, A and B, with s-cis geometry, and the solvate molecule lies on a twofold axis. The core of each molecule is slightly non-planar; the dihedral angles between the conjugated C=C-CN linkage and the phenyl ring, and between this linkage and the thioamide group are 13.4 (2) and 12.0 (2) degrees in (Ia), 14.0 (2) and 18.2 (2) degrees in (Ib), 2.3 (3) and 12.7 (4) degrees in molecule A of (Ic), and 23.2 (3) and 8.1 (4) degrees in molecule B of (Ic). As a result of strong conjugation between donor and acceptor parts, the substituted phenyl rings have noticeable quinoid character. In (Ib), there exists a very strong intramolecular steric interaction (H...H = 1.95 A) between the bridging and thioamide parts of the molecule, which makes such a form less stable. In the crystal structure of (Ia), intermolecular N-H...N and N-H...S hydrogen bonds link molecules into infinite tapes along the [1-10] direction. In (Ib), such intermolecular hydrogen bonds link molecules into infinite (101) planes. In (Ic), intermolecular N-H...N hydrogen bonds link molecules A and B into dimers, which are connected via N-H...S hydrogen bonds and form infinite chains along the c direction.

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Three polar derivatives ofN-ethylcarbazole: materials for optical applications

Cited by 11 publications

References 11 publications

Aromatic/Proaromatic Donors in 2‐Dicyanomethylenethiazole Merocyanines: From Neutral to Strongly Zwitterionic Nonlinear Optical Chromophores

Aromatic/Proaromatic Donors in 2‐Dicyanomethylenethiazole Merocyanines: From Neutral to Strongly Zwitterionic Nonlinear Optical Chromophores

Thermally Stable Imines as New Potential Nonlinear Optical Materials

Polymorphism and solvolysis of 2-cyano-3-[4-(N,N-diethylamino)phenyl]prop-2-enethioamide

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