Solution and Solid-State Photophysical Properties of Positional Isomeric Acrylonitrile Derivatives with Core Pyridine and Phenyl Moieties: Experimental and DFT Studies
The compounds <b>I</b> (<i>Z</i>)-2-(phenyl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile with one side (2,4,5-MeO-), one symmetrical (2<i>Z</i>,2′<i>Z</i>)-2,2′-(1,4-phenylene)bis(3-(2,4,5-trimethoxyphenyl)acrylonitrile), <b>II</b> (both sides...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/6/1500 |
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| author | Armando Castillo Paulina Ceballos Pilar Santos Margarita Cerón Perumal Venkatesan Enrique Pérez-Gutiérrez Martha Sosa-Rivadeneyra Subbiah Thamotharan Maxime A. Siegler María Judith Percino |
| author_facet | Armando Castillo Paulina Ceballos Pilar Santos Margarita Cerón Perumal Venkatesan Enrique Pérez-Gutiérrez Martha Sosa-Rivadeneyra Subbiah Thamotharan Maxime A. Siegler María Judith Percino |
| author_sort | Armando Castillo |
| collection | DOAJ |
| description | The compounds <b>I</b> (<i>Z</i>)-2-(phenyl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile with one side (2,4,5-MeO-), one symmetrical (2<i>Z</i>,2′<i>Z</i>)-2,2′-(1,4-phenylene)bis(3-(2,4,5-trimethoxyphenyl)acrylonitrile), <b>II</b> (both sides with (2,4,5-MeO-), and three positional isomers with pyridine (<i>Z</i>)-2-(pyridin-2- 3, or 4-yl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile, <b>III</b>–<b>V</b> were synthetized and characterized by UV-Vis, fluorescence, IR, H<sup>1</sup>-NMR, and EI mass spectrometry as well as single crystal X-ray diffraction (SCXRD). The optical properties were strongly influenced by the solvent (hyperchromic and hypochromic shift), which were compared with the solid state. According to the solvatochromism theory, the excited-state (<i>μ<sub>e</sub></i>) and ground-state (<i>μ<sub>g</sub></i>) dipole moments were calculated based on the variation of Stokes shift with the solvent’s relative permittivity, refractive index, and polarity parameters. SCXRD analyses revealed that the compounds <b>I</b> and <b>II</b> crystallized in the monoclinic system with the space group, <i>P</i>2<sub>1</sub>/<i>n</i> and <i>P</i>2<sub>1</sub>/<i>c</i>, respectively, and with <i>Z</i> = 4 and 2. <b>III</b>, <b>IV</b>, and <b>V</b> crystallized in space groups: orthorhombic, <i>Pbca</i>; triclinic, <i>P</i>-1; and monoclinic, <i>P</i>2<sub>1</sub> with <i>Z</i> = 1, 2, and 2, respectively. The intermolecular interactions for compounds <b>I</b>–<b>V</b> were investigated using the CCDC Mercury software and their energies were quantified using PIXEL. The density of states (DOS), molecular electrostatic potential surfaces (MEPS), and natural bond orbitals (NBO) of the compounds were determined to evaluate the photophysical properties. |
| first_indexed | 2024-03-10T13:23:05Z |
| format | Article |
| id | doaj.art-4a4885717220435681809f751c4e292a |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T13:23:05Z |
| publishDate | 2021-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-4a4885717220435681809f751c4e292a2023-11-21T09:53:08ZengMDPI AGMolecules1420-30492021-03-01266150010.3390/molecules26061500Solution and Solid-State Photophysical Properties of Positional Isomeric Acrylonitrile Derivatives with Core Pyridine and Phenyl Moieties: Experimental and DFT StudiesArmando Castillo0Paulina Ceballos1Pilar Santos2Margarita Cerón3Perumal Venkatesan4Enrique Pérez-Gutiérrez5Martha Sosa-Rivadeneyra6Subbiah Thamotharan7Maxime A. Siegler8María Judith Percino9Unidad de Polímeros y Electrónica Orgánica, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Val3-Ecocampus Valsequillo, Independencia O2 Sur 50, San Pedro Zacachimalpa 72960, MexicoUnidad de Polímeros y Electrónica Orgánica, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Val3-Ecocampus Valsequillo, Independencia O2 Sur 50, San Pedro Zacachimalpa 72960, MexicoUnidad de Polímeros y Electrónica Orgánica, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Val3-Ecocampus Valsequillo, Independencia O2 Sur 50, San Pedro Zacachimalpa 72960, MexicoUnidad de Polímeros y Electrónica Orgánica, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Val3-Ecocampus Valsequillo, Independencia O2 Sur 50, San Pedro Zacachimalpa 72960, MexicoUnidad de Polímeros y Electrónica Orgánica, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Val3-Ecocampus Valsequillo, Independencia O2 Sur 50, San Pedro Zacachimalpa 72960, MexicoUnidad de Polímeros y Electrónica Orgánica, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Val3-Ecocampus Valsequillo, Independencia O2 Sur 50, San Pedro Zacachimalpa 72960, MexicoFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla (BUAP), 14 Sur Esquina San Claudio, San Manuel, Puebla 72570, MexicoBiomolecular Crystallography Laboratory, School of Chemical & Biotechnology, Department of Bioinformatics, SASTRA Deemed University, Thanjavur 613401, IndiaDepartment of Chemistry, Johns Hopkins University, New Chemistry Building, 3400 N. Charles St., Baltimore, MD 21218, USAUnidad de Polímeros y Electrónica Orgánica, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Val3-Ecocampus Valsequillo, Independencia O2 Sur 50, San Pedro Zacachimalpa 72960, MexicoThe compounds <b>I</b> (<i>Z</i>)-2-(phenyl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile with one side (2,4,5-MeO-), one symmetrical (2<i>Z</i>,2′<i>Z</i>)-2,2′-(1,4-phenylene)bis(3-(2,4,5-trimethoxyphenyl)acrylonitrile), <b>II</b> (both sides with (2,4,5-MeO-), and three positional isomers with pyridine (<i>Z</i>)-2-(pyridin-2- 3, or 4-yl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile, <b>III</b>–<b>V</b> were synthetized and characterized by UV-Vis, fluorescence, IR, H<sup>1</sup>-NMR, and EI mass spectrometry as well as single crystal X-ray diffraction (SCXRD). The optical properties were strongly influenced by the solvent (hyperchromic and hypochromic shift), which were compared with the solid state. According to the solvatochromism theory, the excited-state (<i>μ<sub>e</sub></i>) and ground-state (<i>μ<sub>g</sub></i>) dipole moments were calculated based on the variation of Stokes shift with the solvent’s relative permittivity, refractive index, and polarity parameters. SCXRD analyses revealed that the compounds <b>I</b> and <b>II</b> crystallized in the monoclinic system with the space group, <i>P</i>2<sub>1</sub>/<i>n</i> and <i>P</i>2<sub>1</sub>/<i>c</i>, respectively, and with <i>Z</i> = 4 and 2. <b>III</b>, <b>IV</b>, and <b>V</b> crystallized in space groups: orthorhombic, <i>Pbca</i>; triclinic, <i>P</i>-1; and monoclinic, <i>P</i>2<sub>1</sub> with <i>Z</i> = 1, 2, and 2, respectively. The intermolecular interactions for compounds <b>I</b>–<b>V</b> were investigated using the CCDC Mercury software and their energies were quantified using PIXEL. The density of states (DOS), molecular electrostatic potential surfaces (MEPS), and natural bond orbitals (NBO) of the compounds were determined to evaluate the photophysical properties.https://www.mdpi.com/1420-3049/26/6/1500optical propertiessolution and solid stateacrylonitrile derivativesDFT studiesPIXELMEPS |
| spellingShingle | Armando Castillo Paulina Ceballos Pilar Santos Margarita Cerón Perumal Venkatesan Enrique Pérez-Gutiérrez Martha Sosa-Rivadeneyra Subbiah Thamotharan Maxime A. Siegler María Judith Percino Solution and Solid-State Photophysical Properties of Positional Isomeric Acrylonitrile Derivatives with Core Pyridine and Phenyl Moieties: Experimental and DFT Studies Molecules optical properties solution and solid state acrylonitrile derivatives DFT studies PIXEL MEPS |
| title | Solution and Solid-State Photophysical Properties of Positional Isomeric Acrylonitrile Derivatives with Core Pyridine and Phenyl Moieties: Experimental and DFT Studies |
| title_full | Solution and Solid-State Photophysical Properties of Positional Isomeric Acrylonitrile Derivatives with Core Pyridine and Phenyl Moieties: Experimental and DFT Studies |
| title_fullStr | Solution and Solid-State Photophysical Properties of Positional Isomeric Acrylonitrile Derivatives with Core Pyridine and Phenyl Moieties: Experimental and DFT Studies |
| title_full_unstemmed | Solution and Solid-State Photophysical Properties of Positional Isomeric Acrylonitrile Derivatives with Core Pyridine and Phenyl Moieties: Experimental and DFT Studies |
| title_short | Solution and Solid-State Photophysical Properties of Positional Isomeric Acrylonitrile Derivatives with Core Pyridine and Phenyl Moieties: Experimental and DFT Studies |
| title_sort | solution and solid state photophysical properties of positional isomeric acrylonitrile derivatives with core pyridine and phenyl moieties experimental and dft studies |
| topic | optical properties solution and solid state acrylonitrile derivatives DFT studies PIXEL MEPS |
| url | https://www.mdpi.com/1420-3049/26/6/1500 |
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