Novel Dihydro-1,3,<i>2H</i>-benzoxazine Derived from Furfurylamine: Crystal Structure, Hirshfeld Surface Analysis, Photophysical Property, and Computational Study
Dihydro-1,3,<i>2H</i>-benzoxazines (or benzoxazine monomers) are a class of compounds that have been widely utilized in many areas such as the production of the functional polymers and optoelectronic materials. The structure variety of the benzoxazines plays a vital role in their desired...
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MDPI AG
2021-05-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/11/5/568 |
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| author | Worawat Wattanathana Yuranan Hanlumyuang Suttipong Wannapaiboon Kantapat Chansaenpak Piyanut Pinyou Tanin Nanok Pongsakorn Kanjanaboos |
| author_facet | Worawat Wattanathana Yuranan Hanlumyuang Suttipong Wannapaiboon Kantapat Chansaenpak Piyanut Pinyou Tanin Nanok Pongsakorn Kanjanaboos |
| author_sort | Worawat Wattanathana |
| collection | DOAJ |
| description | Dihydro-1,3,<i>2H</i>-benzoxazines (or benzoxazine monomers) are a class of compounds that have been widely utilized in many areas such as the production of the functional polymers and optoelectronic materials. The structure variety of the benzoxazines plays a vital role in their desired properties. The effort of synthesizing functionalized benzoxazines from bioresources is of interest for sustainable development. Herein, we report the synthesis of the novel benzoxazine monomer referred to as 3-(furan-2-ylmethyl)-6-methyl-3,4-dihydro-<i>2H</i>-benzo[<i>e</i>][1,3]oxazine or benzoxazine (I) from a one-pot Mannich reaction using <i>p</i>-cresol, paraformaldehyde, and furfurylamine (a bio-derived amine). An X-ray crystallographic study was performed at low temperature (100 K) to obtain the structural characteristics of the benzoxazine (I). The result reveals that the oxazine ring adopts a half chair conformation to locate all the members of the benzoxazine ring as planar as possible by employing the expansion of the bond angles within the ring. Apart from the structural parameters, the intermolecular interactions were also examined. It was found that the significant interactions within the crystal are C–H···N, C–H···O, and the C–H···π interactions. The C–H···N interactions link the benzoxazine (I) molecules into an infinite molecular chain, propagating along the [100] direction. Hirshfeld surfaces and their corresponding fingerprint plots were comprehensively analyzed to confirm and quantify the significance of these interactions. Moreover, the photophysical properties of the benzoxazine (I) were investigated in solvents with various polarities. The corresponding relations between the structural features, frontier molecular orbitals, and absorption-and-emission characteristics were proposed and explained according to the DFT and TD-DFT calculations. |
| first_indexed | 2024-03-10T11:15:37Z |
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| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-10T11:15:37Z |
| publishDate | 2021-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-dcc4ba5751cb4d5c9887c605e67d8ccf2023-11-21T20:30:44ZengMDPI AGCrystals2073-43522021-05-0111556810.3390/cryst11050568Novel Dihydro-1,3,<i>2H</i>-benzoxazine Derived from Furfurylamine: Crystal Structure, Hirshfeld Surface Analysis, Photophysical Property, and Computational StudyWorawat Wattanathana0Yuranan Hanlumyuang1Suttipong Wannapaiboon2Kantapat Chansaenpak3Piyanut Pinyou4Tanin Nanok5Pongsakorn Kanjanaboos6Department of Materials Engineering, Faculty of Engineering, Kasetsart University, Bangkok 10900, ThailandDepartment of Materials Engineering, Faculty of Engineering, Kasetsart University, Bangkok 10900, ThailandSynchrotron Light Research Institute, 111 University Avenue, Nakhon Ratchasima 30000, ThailandNational Nanotechnology Center, National Science and Technology Development Agency, Thailand Science Park, Pathum Thani 12120, ThailandSchool of Chemistry, Institute of Science, Suranaree University of Technology, 111 University Avenue, Nakhon Ratchasima 30000, ThailandDepartment of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, ThailandSchool of Materials Science and Innovation, Faculty of Science, Mahidol University, Bangkok 10400, ThailandDihydro-1,3,<i>2H</i>-benzoxazines (or benzoxazine monomers) are a class of compounds that have been widely utilized in many areas such as the production of the functional polymers and optoelectronic materials. The structure variety of the benzoxazines plays a vital role in their desired properties. The effort of synthesizing functionalized benzoxazines from bioresources is of interest for sustainable development. Herein, we report the synthesis of the novel benzoxazine monomer referred to as 3-(furan-2-ylmethyl)-6-methyl-3,4-dihydro-<i>2H</i>-benzo[<i>e</i>][1,3]oxazine or benzoxazine (I) from a one-pot Mannich reaction using <i>p</i>-cresol, paraformaldehyde, and furfurylamine (a bio-derived amine). An X-ray crystallographic study was performed at low temperature (100 K) to obtain the structural characteristics of the benzoxazine (I). The result reveals that the oxazine ring adopts a half chair conformation to locate all the members of the benzoxazine ring as planar as possible by employing the expansion of the bond angles within the ring. Apart from the structural parameters, the intermolecular interactions were also examined. It was found that the significant interactions within the crystal are C–H···N, C–H···O, and the C–H···π interactions. The C–H···N interactions link the benzoxazine (I) molecules into an infinite molecular chain, propagating along the [100] direction. Hirshfeld surfaces and their corresponding fingerprint plots were comprehensively analyzed to confirm and quantify the significance of these interactions. Moreover, the photophysical properties of the benzoxazine (I) were investigated in solvents with various polarities. The corresponding relations between the structural features, frontier molecular orbitals, and absorption-and-emission characteristics were proposed and explained according to the DFT and TD-DFT calculations.https://www.mdpi.com/2073-4352/11/5/568crystal structureHirshfeld surface analysisphotophysical propertiesbenzoxazine |
| spellingShingle | Worawat Wattanathana Yuranan Hanlumyuang Suttipong Wannapaiboon Kantapat Chansaenpak Piyanut Pinyou Tanin Nanok Pongsakorn Kanjanaboos Novel Dihydro-1,3,<i>2H</i>-benzoxazine Derived from Furfurylamine: Crystal Structure, Hirshfeld Surface Analysis, Photophysical Property, and Computational Study Crystals crystal structure Hirshfeld surface analysis photophysical properties benzoxazine |
| title | Novel Dihydro-1,3,<i>2H</i>-benzoxazine Derived from Furfurylamine: Crystal Structure, Hirshfeld Surface Analysis, Photophysical Property, and Computational Study |
| title_full | Novel Dihydro-1,3,<i>2H</i>-benzoxazine Derived from Furfurylamine: Crystal Structure, Hirshfeld Surface Analysis, Photophysical Property, and Computational Study |
| title_fullStr | Novel Dihydro-1,3,<i>2H</i>-benzoxazine Derived from Furfurylamine: Crystal Structure, Hirshfeld Surface Analysis, Photophysical Property, and Computational Study |
| title_full_unstemmed | Novel Dihydro-1,3,<i>2H</i>-benzoxazine Derived from Furfurylamine: Crystal Structure, Hirshfeld Surface Analysis, Photophysical Property, and Computational Study |
| title_short | Novel Dihydro-1,3,<i>2H</i>-benzoxazine Derived from Furfurylamine: Crystal Structure, Hirshfeld Surface Analysis, Photophysical Property, and Computational Study |
| title_sort | novel dihydro 1 3 i 2h i benzoxazine derived from furfurylamine crystal structure hirshfeld surface analysis photophysical property and computational study |
| topic | crystal structure Hirshfeld surface analysis photophysical properties benzoxazine |
| url | https://www.mdpi.com/2073-4352/11/5/568 |
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