Synthesis, Optical Characterization in Solution and Solid-State, and DFT Calculations of 3-Acetyl and 3-(1′-(2′-Phenylhydrazono)ethyl)-coumarin-(7)-substituted Derivatives
Intramolecular charge transfer (ICT) effects are responsible for the photoluminescent properties of coumarins. Hence, optical properties with different applications can be obtained by ICT modulation. Herein, four 3-acetyl-2<i>H</i>-chromen-2-ones (<b>1a</b>–<b>d</b&g...
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| Format: | Article |
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MDPI AG
2022-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/12/3677 |
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| author | Cesar A. Villa-Martínez Nancy E. Magaña-Vergara Mario Rodríguez Juan P. Mojica-Sánchez Ángel A. Ramos-Organillo Joaquín Barroso-Flores Itzia I. Padilla-Martínez Francisco J. Martínez-Martínez |
| author_facet | Cesar A. Villa-Martínez Nancy E. Magaña-Vergara Mario Rodríguez Juan P. Mojica-Sánchez Ángel A. Ramos-Organillo Joaquín Barroso-Flores Itzia I. Padilla-Martínez Francisco J. Martínez-Martínez |
| author_sort | Cesar A. Villa-Martínez |
| collection | DOAJ |
| description | Intramolecular charge transfer (ICT) effects are responsible for the photoluminescent properties of coumarins. Hence, optical properties with different applications can be obtained by ICT modulation. Herein, four 3-acetyl-2<i>H</i>-chromen-2-ones (<b>1a</b>–<b>d</b>) and their corresponding fluorescent hybrids 3- (phenylhydrazone)-chromen-2-ones (<b>2a</b>–<b>d</b>) were synthesized in 74–65% yields. The UV-Vis data were in the 295–428 nm range. The emission depends on the substituent in position C-7 bearing electron-donating groups. Compounds <b>1b</b>–<b>d</b> showed good optical properties due to the D-π-A structural arrangement. In compounds <b>2a</b>–<b>d</b>, there is a quenching effect of fluorescence in solution. However, in the solid, an increase is shown due to an aggregation-induced emission (AIE) effect given by the rotational restraints and stacking in the crystal. Computational calculations of the HOMO-LUMO orbitals indicate high absorbance and emission values of the molecules, and gap values represent the bathochromic effect and the electronic efficiency of the compounds. Compounds <b>1a</b>–<b>d</b> and <b>2a</b>–<b>d</b> are good candidates for optical applications, such as OLEDs, organic solar cells, or fluorescence markers. |
| first_indexed | 2024-03-09T22:56:51Z |
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| id | doaj.art-286d36f1b2c346c4936a862c29a911ef |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T22:56:51Z |
| publishDate | 2022-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-286d36f1b2c346c4936a862c29a911ef2023-11-23T18:09:21ZengMDPI AGMolecules1420-30492022-06-012712367710.3390/molecules27123677Synthesis, Optical Characterization in Solution and Solid-State, and DFT Calculations of 3-Acetyl and 3-(1′-(2′-Phenylhydrazono)ethyl)-coumarin-(7)-substituted DerivativesCesar A. Villa-Martínez0Nancy E. Magaña-Vergara1Mario Rodríguez2Juan P. Mojica-Sánchez3Ángel A. Ramos-Organillo4Joaquín Barroso-Flores5Itzia I. Padilla-Martínez6Francisco J. Martínez-Martínez7Facultad de Ciencias Químicas, Universidad de Colima, Km 9 Carretera Coquimatlán-Colima, Coquimatlán 28400, MexicoCONACyT, Facultad de Ciencias Químicas, Universidad de Colima, Km 9 Carretera Coquimatlán-Colima, Coquimatlán 28400, MexicoCentro de Investigaciones en Óptica A. P. 1-948, León 37000, MexicoTecnológico Nacional de Mexico, Instituto Tecnológico José Mario Molina Pasquel y Henríquez Campus Tamazula de Gordiano, Carretera Tamazula-Santa Rosa No. 329, Tamazula de Gordiano 49650, MexicoFacultad de Ciencias Químicas, Universidad de Colima, Km 9 Carretera Coquimatlán-Colima, Coquimatlán 28400, MexicoCentro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Unidad San Cayetano, Carretera Toluca-Atlacomulco Km.14.5, Toluca de Lerdo 50200, MexicoLaboratorio de Química Supramolecular y Nanociencias, UPIBI, Instituto Politécnico Nacional, Av. Acueducto s/n Barrio la Laguna Ticomán, Ciudad de Mexico 07340, MexicoFacultad de Ciencias Químicas, Universidad de Colima, Km 9 Carretera Coquimatlán-Colima, Coquimatlán 28400, MexicoIntramolecular charge transfer (ICT) effects are responsible for the photoluminescent properties of coumarins. Hence, optical properties with different applications can be obtained by ICT modulation. Herein, four 3-acetyl-2<i>H</i>-chromen-2-ones (<b>1a</b>–<b>d</b>) and their corresponding fluorescent hybrids 3- (phenylhydrazone)-chromen-2-ones (<b>2a</b>–<b>d</b>) were synthesized in 74–65% yields. The UV-Vis data were in the 295–428 nm range. The emission depends on the substituent in position C-7 bearing electron-donating groups. Compounds <b>1b</b>–<b>d</b> showed good optical properties due to the D-π-A structural arrangement. In compounds <b>2a</b>–<b>d</b>, there is a quenching effect of fluorescence in solution. However, in the solid, an increase is shown due to an aggregation-induced emission (AIE) effect given by the rotational restraints and stacking in the crystal. Computational calculations of the HOMO-LUMO orbitals indicate high absorbance and emission values of the molecules, and gap values represent the bathochromic effect and the electronic efficiency of the compounds. Compounds <b>1a</b>–<b>d</b> and <b>2a</b>–<b>d</b> are good candidates for optical applications, such as OLEDs, organic solar cells, or fluorescence markers.https://www.mdpi.com/1420-3049/27/12/3677coumarinshydrazonesoptical propertiesHOMO-LUMO orbitals |
| spellingShingle | Cesar A. Villa-Martínez Nancy E. Magaña-Vergara Mario Rodríguez Juan P. Mojica-Sánchez Ángel A. Ramos-Organillo Joaquín Barroso-Flores Itzia I. Padilla-Martínez Francisco J. Martínez-Martínez Synthesis, Optical Characterization in Solution and Solid-State, and DFT Calculations of 3-Acetyl and 3-(1′-(2′-Phenylhydrazono)ethyl)-coumarin-(7)-substituted Derivatives Molecules coumarins hydrazones optical properties HOMO-LUMO orbitals |
| title | Synthesis, Optical Characterization in Solution and Solid-State, and DFT Calculations of 3-Acetyl and 3-(1′-(2′-Phenylhydrazono)ethyl)-coumarin-(7)-substituted Derivatives |
| title_full | Synthesis, Optical Characterization in Solution and Solid-State, and DFT Calculations of 3-Acetyl and 3-(1′-(2′-Phenylhydrazono)ethyl)-coumarin-(7)-substituted Derivatives |
| title_fullStr | Synthesis, Optical Characterization in Solution and Solid-State, and DFT Calculations of 3-Acetyl and 3-(1′-(2′-Phenylhydrazono)ethyl)-coumarin-(7)-substituted Derivatives |
| title_full_unstemmed | Synthesis, Optical Characterization in Solution and Solid-State, and DFT Calculations of 3-Acetyl and 3-(1′-(2′-Phenylhydrazono)ethyl)-coumarin-(7)-substituted Derivatives |
| title_short | Synthesis, Optical Characterization in Solution and Solid-State, and DFT Calculations of 3-Acetyl and 3-(1′-(2′-Phenylhydrazono)ethyl)-coumarin-(7)-substituted Derivatives |
| title_sort | synthesis optical characterization in solution and solid state and dft calculations of 3 acetyl and 3 1 2 phenylhydrazono ethyl coumarin 7 substituted derivatives |
| topic | coumarins hydrazones optical properties HOMO-LUMO orbitals |
| url | https://www.mdpi.com/1420-3049/27/12/3677 |
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