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

dc.contributor.authorSouza, Talita Evelyn
dc.contributor.authorRosa, Iara Maria Landre
dc.contributor.authorLegendre, Alexandre Oliveira [UNESP]
dc.contributor.authorPaschoal, Diego
dc.contributor.authorMaia, Lauro June Queiroz
dc.contributor.authorSantos, Hélio Ferreira dos
dc.contributor.authorMatins, Felipe Terra
dc.contributor.authorDoriguetto, Antonio Carlos
dc.contributor.institutionUniversidade Federal de Alfenas (UNIFAL)
dc.contributor.institutionUniversidade Estadual Paulista (Unesp)
dc.contributor.institutionUniversidade Federal de Juiz de Fora (UFJF)
dc.contributor.institutionUniversidade Federal de Goiás (UFG)
dc.date.accessioned2015-12-07T15:35:45Z
dc.date.available2015-12-07T15:35:45Z
dc.date.issued2015
dc.description.abstractThree 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.en
dc.description.affiliationInstituto de Química, Universidade Federal de Alfenas (UNIFAL), Alfenas, MG, Brasil
dc.description.affiliationFaculdade de Ciências (FC), Universidade Estadual Paulista (UNESP), Bauru, SP, Brasil
dc.description.affiliationDepartamento de Química, ICE, Universidade Federal de Juiz de Fora (UFJF), Juiz de Fora, MG, Brasil
dc.description.affiliationInstituto de Física, Universidade Federal de Goiás (UFG), Goiânia, GO, Brasil
dc.description.affiliationInstituto de Química, Universidade Federal de Goiás (UFG), Goiânia, GO, Brasil
dc.description.affiliationUnespFaculdade de Ciências (FC), Universidade Estadual Paulista (UNESP), Bauru, SP, Brasil
dc.description.sponsorshipFinanciadora de Estudos e Projetos (FINEP)
dc.description.sponsorshipConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
dc.description.sponsorshipCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
dc.description.sponsorshipFundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG)
dc.description.sponsorshipIdFINEP: 134/08
dc.description.sponsorshipIdCNPq: 476870/2011-9
dc.description.sponsorshipIdCNPq: 308354/2012-5
dc.description.sponsorshipIdCNPq: 448723/2014-0
dc.description.sponsorshipIdCAPES: AUX-PE-PNPD-1865/2008
dc.description.sponsorshipIdFAPEMIG: PRONEX APQ-04730-10
dc.description.sponsorshipIdFAPEMIG: APQ-01093-10
dc.description.sponsorshipIdFAPEMIG: APQ-02600-12
dc.description.sponsorshipIdFAPEMIG: BPD-00060-14
dc.description.sponsorshipIdFAPEMIG: PPM-00524-12
dc.description.sponsorshipIdFAPEMIG: APQ-02486-14
dc.format.extent416-426
dc.identifierhttp://dx.doi.org/10.1107/S2052520615008859
dc.identifier.citationActa Crystallographica Section B, Structural Science, Crystal Engineering and Materials, v. 71, n. pt 4, p. 416-426, 2015.
dc.identifier.doi10.1107/S2052520615008859
dc.identifier.issn2052-5206
dc.identifier.pubmed26208622
dc.identifier.urihttp://hdl.handle.net/11449/131454
dc.language.isoeng
dc.publisherInternational Union of Crystallography
dc.relation.ispartofActa Crystallographica Section B, Structural Science, Crystal Engineering And Materials
dc.relation.ispartofjcr6.467
dc.relation.ispartofsjr1,654
dc.rights.accessRightsAcesso restrito
dc.sourcePubMed
dc.subjectN-benzylideneaniline derivativesen
dc.subjectElectron–push–pullen
dc.subjectNon-centrosymmetric crystalsen
dc.subjectNon-linear opticsen
dc.titleNon-centrosymmetric crystals of new N-benzylideneaniline derivatives as potential materials for non-linear opticsen
dc.typeArtigo
dcterms.rightsHolderInternational Union of Crystallography
unesp.author.lattes3123518117881050[3]
unesp.author.orcid0000-0002-2794-5763[3]
unesp.campusUniversidade Estadual Paulista (Unesp), Faculdade de Ciências, Baurupt
unesp.departmentQuímica - FCpt

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