Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies
In this work, two oligophenyleneimines type pentamers with terminal aldehydes, designated as DAFCHO (4,4′-((((((2,5-bis(octyloxy)-1,4-phenylene)bis(methanylylidene))bis(azanyl ylidene))bis(9H-fluorene-7,2-diyl))bis(azanylylidene))bis(methanylylidene))bis(2,5-bis(octyloxy) benzaldehyde)) an...
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MDPI AG
2019-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/5/849 |
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| author | Miguel Angel Amado-Briseño Luis Ángel Zárate-Hernández Karina Alemán-Ayala Oscar Coreño Alonso Julián Cruz-Borbolla José Manuel Vásquez-Pérez Víctor Esteban Reyes-Cruz María Aurora Veloz-Rodríguez Esteban Rueda-Soriano Thangarasu Pandiyan Rosa Angeles Vázquez-García |
| author_facet | Miguel Angel Amado-Briseño Luis Ángel Zárate-Hernández Karina Alemán-Ayala Oscar Coreño Alonso Julián Cruz-Borbolla José Manuel Vásquez-Pérez Víctor Esteban Reyes-Cruz María Aurora Veloz-Rodríguez Esteban Rueda-Soriano Thangarasu Pandiyan Rosa Angeles Vázquez-García |
| author_sort | Miguel Angel Amado-Briseño |
| collection | DOAJ |
| description | In this work, two oligophenyleneimines type pentamers with terminal aldehydes, designated as DAFCHO (4,4′-((((((2,5-bis(octyloxy)-1,4-phenylene)bis(methanylylidene))bis(azanyl ylidene))bis(9H-fluorene-7,2-diyl))bis(azanylylidene))bis(methanylylidene))bis(2,5-bis(octyloxy) benzaldehyde)) and FDACHO (4,4′-((((((2,5-bis(octyloxy)-1,4-phenylene)bis(methanylylidene))bis (azanylylidene))bis(4,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(2,5-bis(octyloxy) benzaldehyde)) were synthesized by mechanochemistry method using 2,5-bis(octyloxy) terephtal aldehyde and 2,7-diaminofluorene or 1,4-phenylenediamine. All compounds were spectroscopically characterized using <sup>1</sup>H and <sup>13</sup>C-NMR, FT-IR and mass spectrometry MALDITOF. The optical properties of the compounds were analyzed by UV-vis spectroscopy using different solvents. We observed that DAFCHO and FDACHO exhibit interesting photochromic properties when they are dissolved in chloroform and exposed to sunlight for 3, 5 and 10 min. The value of the energy band gap was calculated from the absorption spectra without irradiation E<sub>gap(optical)</sub>. It was 2.50 eV for DAFCHO in chloroform solution, and it decreased to 2.34 eV when it is in films. For FDACHO, it was 2.41 eV in solution and 2.27 eV in film. HOMO (Highest Occupied Molecular Orbital), LUMO (Lowest Unoccupied Molecular Orbital) and E<sub>gap(electrochemical)</sub> values were obtained by electrochemical studies. The results indicate that the compounds can be considered as organic semiconductors since their values are 2.35 eV for DAFCHO and 2.06 eV for FDACHO. The structural and electronic properties of the compounds were corroborated with a DFT (Density Functional Theory) study. |
| first_indexed | 2024-12-12T03:07:02Z |
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| last_indexed | 2024-12-12T03:07:02Z |
| publishDate | 2019-02-01 |
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| spelling | doaj.art-190347a2c89445b68c8a01c8534856e12022-12-22T00:40:30ZengMDPI AGMolecules1420-30492019-02-0124584910.3390/molecules24050849molecules24050849Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical StudiesMiguel Angel Amado-Briseño0Luis Ángel Zárate-Hernández1Karina Alemán-Ayala2Oscar Coreño Alonso3Julián Cruz-Borbolla4José Manuel Vásquez-Pérez5Víctor Esteban Reyes-Cruz6María Aurora Veloz-Rodríguez7Esteban Rueda-Soriano8Thangarasu Pandiyan9Rosa Angeles Vázquez-García10Área Académica de Ciencias de la Tierra y Materiales, Área Académica de Computación y Electrónica, Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Pachuca CP 42184, MexicoÁrea Académica de Ciencias de la Tierra y Materiales, Área Académica de Computación y Electrónica, Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Pachuca CP 42184, MexicoÁrea Académica de Ciencias de la Tierra y Materiales, Área Académica de Computación y Electrónica, Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Pachuca CP 42184, MexicoDpto. Ing. Civil, Universidad de Guanajuato, Juárez 77, Guanajuato CP 36000, MexicoÁrea Académica de Ciencias de la Tierra y Materiales, Área Académica de Computación y Electrónica, Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Pachuca CP 42184, MexicoÁrea Académica de Ciencias de la Tierra y Materiales, Área Académica de Computación y Electrónica, Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Pachuca CP 42184, MexicoÁrea Académica de Ciencias de la Tierra y Materiales, Área Académica de Computación y Electrónica, Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Pachuca CP 42184, MexicoÁrea Académica de Ciencias de la Tierra y Materiales, Área Académica de Computación y Electrónica, Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Pachuca CP 42184, MexicoÁrea Académica de Ciencias de la Tierra y Materiales, Área Académica de Computación y Electrónica, Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Pachuca CP 42184, MexicoFacultad de Química, UNAM, Cd. Universitaria, Circuito exterior, Coyoacán, México D.F. CP 04510, MexicoÁrea Académica de Ciencias de la Tierra y Materiales, Área Académica de Computación y Electrónica, Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Pachuca CP 42184, MexicoIn this work, two oligophenyleneimines type pentamers with terminal aldehydes, designated as DAFCHO (4,4′-((((((2,5-bis(octyloxy)-1,4-phenylene)bis(methanylylidene))bis(azanyl ylidene))bis(9H-fluorene-7,2-diyl))bis(azanylylidene))bis(methanylylidene))bis(2,5-bis(octyloxy) benzaldehyde)) and FDACHO (4,4′-((((((2,5-bis(octyloxy)-1,4-phenylene)bis(methanylylidene))bis (azanylylidene))bis(4,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(2,5-bis(octyloxy) benzaldehyde)) were synthesized by mechanochemistry method using 2,5-bis(octyloxy) terephtal aldehyde and 2,7-diaminofluorene or 1,4-phenylenediamine. All compounds were spectroscopically characterized using <sup>1</sup>H and <sup>13</sup>C-NMR, FT-IR and mass spectrometry MALDITOF. The optical properties of the compounds were analyzed by UV-vis spectroscopy using different solvents. We observed that DAFCHO and FDACHO exhibit interesting photochromic properties when they are dissolved in chloroform and exposed to sunlight for 3, 5 and 10 min. The value of the energy band gap was calculated from the absorption spectra without irradiation E<sub>gap(optical)</sub>. It was 2.50 eV for DAFCHO in chloroform solution, and it decreased to 2.34 eV when it is in films. For FDACHO, it was 2.41 eV in solution and 2.27 eV in film. HOMO (Highest Occupied Molecular Orbital), LUMO (Lowest Unoccupied Molecular Orbital) and E<sub>gap(electrochemical)</sub> values were obtained by electrochemical studies. The results indicate that the compounds can be considered as organic semiconductors since their values are 2.35 eV for DAFCHO and 2.06 eV for FDACHO. The structural and electronic properties of the compounds were corroborated with a DFT (Density Functional Theory) study.https://www.mdpi.com/1420-3049/24/5/849mechanochemistryoligophenyleneiminesphotochromicstheoretical calculations |
| spellingShingle | Miguel Angel Amado-Briseño Luis Ángel Zárate-Hernández Karina Alemán-Ayala Oscar Coreño Alonso Julián Cruz-Borbolla José Manuel Vásquez-Pérez Víctor Esteban Reyes-Cruz María Aurora Veloz-Rodríguez Esteban Rueda-Soriano Thangarasu Pandiyan Rosa Angeles Vázquez-García Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies Molecules mechanochemistry oligophenyleneimines photochromics theoretical calculations |
| title | Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies |
| title_full | Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies |
| title_fullStr | Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies |
| title_full_unstemmed | Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies |
| title_short | Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies |
| title_sort | mechanosynthesis of photochromic oligophenyleneimines optical electrochemical and theoretical studies |
| topic | mechanochemistry oligophenyleneimines photochromics theoretical calculations |
| url | https://www.mdpi.com/1420-3049/24/5/849 |
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