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Molecules 2016, 21(4), 389; doi:10.3390/molecules21040389

Conformational and Molecular Structures of α,β-Unsaturated Acrylonitrile Derivatives: Photophysical Properties and Their Frontier Orbitals

1
Laboratorio de Polímeros, Centro de Química, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla (BUAP), Complejo de Ciencias, ICUAP, Edif. 103H, 22 Sur y San Claudio, C.P. 72570 Puebla, Puebla, Mexico
2
Department of Chemistry, Johns Hopkins University, New Chemistry Building, 3400 N. Charles St. Baltimore, MD 21218, USA
3
Centro de Investigaciones en Óptica (CIO), Loma del Bosque 115, Lomas del Campestre, León, Guanajuato 37000, Mexico
*
Author to whom correspondence should be addressed.
Academic Editors: Scott Reed and Marino Resendiz
Received: 8 January 2016 / Revised: 10 March 2016 / Accepted: 15 March 2016 / Published: 28 March 2016
(This article belongs to the Special Issue Photoactive Molecules)
View Full-Text   |   Download PDF [5851 KB, uploaded 28 March 2016]   |  

Abstract

We report single crystal X-ray diffraction (hereafter, SCXRD) analyses of derivatives featuring the electron-donor N-ethylcarbazole or the (4-diphenylamino)phenyl moieties associated with a -CN group attached to a double bond. The compounds are (2Z)-3-(4-(diphenylamino)-phenyl)-2-(pyridin-3-yl)prop-2-enenitrile (I), (2Z)-3-(4-(diphenylamino)phenyl)-2-(pyridin-4-yl)-prop-2-enenitrile (II) and (2Z)-3-(9-ethyl-9H-carbazol-3-yl)-2-(pyridin-2-yl)enenitrile (III). SCXRD analyses reveal that I and III crystallize in the monoclinic space groups P2/c with Z’ = 2 and C2/c with Z’ = 1, respectively. Compound II crystallized in the orthorhombic space group Pbcn with Z’ = 1. The molecular packing analysis was conducted to examine the pyridine core effect, depending on the ortho, meta- and para-positions of the nitrogen atom, with respect to the optical properties and number of independent molecules (Z’). It is found that the double bond bearing a diphenylamino moiety introduced properties to exhibit a strong π-π-interaction in the solid state. The compounds were examined to evaluate the effects of solvent polarity, the role of the molecular structure, and the molecular interactions on their self-assembly behaviors. Compound I crystallized with a cell with two conformers, anti and syn, due to interaction with solvent. DFT calculations indicated the anti and syn structures of I are energetically stable (less than 1 eV). Also electrochemical and photophysical properties of the compounds were investigated, as well as the determination of optimization calculations in gas and different solvent (chloroform, cyclohexane, methanol, ethanol, tetrahydrofuran, dichloromethane and dimethyl sulfoxide) in the Gaussian09 program. The effect of solvent by PCM method was also investigated. The frontier HOMO and LUMO energies and gap energies are reported. View Full-Text
Keywords: structure-property relationships; electrochemical properties; charge transfer; supramolecular network; D-π-A type dyes and DFT calculations structure-property relationships; electrochemical properties; charge transfer; supramolecular network; D-π-A type dyes and DFT calculations
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MDPI and ACS Style

Percino, M.J.; Cerón, M.; Rodríguez, O.; Soriano-Moro, G.; Castro, M.E.; Chapela, V.M.; Siegler, M.A.; Pérez-Gutiérrez, E. Conformational and Molecular Structures of α,β-Unsaturated Acrylonitrile Derivatives: Photophysical Properties and Their Frontier Orbitals. Molecules 2016, 21, 389.

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