Systematic study of polymorphism in crystalline non-linear optical materials

Timofeeva, Tatiana V.; Нестеров, В. Н.; Clark, Ronald D.; Penn, Benjamin G.; Frazier, Donald O.; Antipin, M. Yu.

doi:10.1016/s0022-2860(02)00523-9

Cited by 28 publications

(21 citation statements)

References 31 publications

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“…The centrosymmetric triclinic (denoted 1t) and noncentrosymmetric orthorhombic crystals (denoted 1r) were found to be in an equal ratio. The concomitant crystallization of centrosymmetric and noncentrosymmetric polymorphs is a rare phenomenon and has been studied with respect to organic nonlinear optical (NLO) materials (Timofeeva et al, 2000(Timofeeva et al, , 2003Jha et al, 2018) and 3-(3-phenyl-1H-1,2,4-triazol-5yl)-2H-1-benzopyran-2-one (Shishkina et al, 2019).…”

Section: Crystallizationmentioning

confidence: 99%

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole

Shishkina

Konovalova

Karpina

et al. 2020

Acta Crystallogr C Struct Chem

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The dipharmacophore compound 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole, C10H11N5O, was studied on the assumption of its potential biological activity. Two concomitant polymorphs were obtained on crystallization from isopropanol solution and these were thoroughly studied. Identical conformations of the molecules are found in both structures despite the low difference in energy between the four possible conformers. The two polymorphs differ crucially with respect to their crystal structures. A centrosymmetric dimer formed due to both stacking interactions of the `head-to-tail' type and N—H...N(π) hydrogen bonds is the building unit in the triclinic structure. The dimeric building units form an isotropic packing. In the orthorhombic polymorphic structure, the molecules form stacking interactions of the `head-to-head' type, which results in their organization in a column as the primary basic structural motif. The formation of N—H...N(lone pair) hydrogen bonds between two neighbouring columns allows the formation of a double column as the main structural motif. The correct packing motifs in the two polymorphs could not be identified without calculations of the pairwise interaction energies. The triclinic structure has a higher density and a lower (by 0.60 kcal mol−1) lattice energy according to periodic calculations compared to the orthorhombic structure. This allows us to presume that the triclinic form of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole is the more stable.

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Section: Crystallizationmentioning

confidence: 99%

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole

Shishkina

Konovalova

Karpina

et al. 2020

Acta Crystallogr C Struct Chem

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“…Organic materials have continuously been under investigation, as their potential NLO efficiency can be significantly higher than that of inorganic materials (Ji et al, 2013;Thomas et al, 2015;Alen et al, 2013). Besides having a polarizable -cloud with electron-donating and -accepting groups, an essential feature for an NLO response of such compounds in the solid state is that they must crystallize in non-centrosymmetric space groups (Draguta et al, 2013;Timofeeva et al, 2003). This requirement is considered a challenge in crystal engineering applied to crystalline NLO materials.…”

Section: Introductionmentioning

confidence: 99%

Non-centrosymmetric crystals of newN-benzylideneaniline derivatives as potential materials for non-linear optics

Souza

Rosa

Legendre

et al. 2015

Acta Crystallogr Sect B

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Three new N-benzylideneaniline derivatives [p-nitrobenzylidene-p-phenylamineaniline (I), 2,4-dinitrobenzylidene-p-phenylamineaniline (II) and p-dinitrobenzylidene-p-diethylamineaniline (III)] containing electron-push-pull groups have been prepared. They present a planar N-benzylideneaniline core and neighbouring functional atoms, which are related through an efficient intramolecular charge transfer (CT). Two of the derivatives crystallize in non-centrosymmetric space groups, a necessary condition for non-linear optical (NLO) responses. The NLO properties were calculated for the molecular conformations determined by single-crystal X-ray diffraction as well as for the four molecules packed into each corresponding unit cell, using a quantum-chemical method at the cam-B3LYP/NLO-V level of theory. As expected from antiparallel face-to-face stacking through centrosymmetry, the main NLO descriptors - namely, the first hyperpolarizability (βtot) and its projection on the dipole moment direction (βvec) - are almost zero for the tetramer of derivative III. Interestingly, the calculated first hyperpolarizability decreases in the non-centrosymmetric unit-cell content of derivative II when compared to its single molecule, which may be related to its molecular pillaring, similar to that observed in derivative III. On the other hand, a desirable magnification of the NLO properties was found for packed units of derivative I, which may be a consequence of its parallel face-to-tail stacking with the CT vectors of all molecules pointing in the same direction. Moreover, the CT vector of compound I makes an angle of θ = 33.6° with its crystal polar axis, resulting in a higher-order parameter (cos(3)θ = 0.6) compared with the other derivatives. This is in line with the higher macroscopic second-order NLO response predicted for derivative I, βtot = 120.4 × 10(-30) e.s.u.

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“…also gives an opportunity to obtain acentric NLO crystals. [15][16][17] Another strategy to encourage polar organic molecules to be crystallized in acentric space groups is the use of strong [18][19][20] and even weak 21 hydrogen-bond interactions. We used the latter strategy in our present study for formation of acentric NLO crystalline materials.…”

Section: Introductionmentioning

confidence: 99%

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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Systematic study of polymorphism in crystalline non-linear optical materials

Cited by 28 publications

References 31 publications

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole

Concomitant polymorphic forms of 3-cyclopropyl-5-(2-hydrazinylpyridin-3-yl)-1,2,4-oxadiazole

Non-centrosymmetric crystals of newN-benzylideneaniline derivatives as potential materials for non-linear optics

Thermally Stable Imines as New Potential Nonlinear Optical Materials

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