Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in Tetrathiafulvalenylallene
Dissymmetric 1,3-diphenylallene derivative 3 connected with 4,5-bis(methyl-thio)tetrathiafulvalenyl and 1-pyrenyl substituents was prepared and characterized. The molecular structure was determined by X-ray crystallographic analysis. Optical resolution was accomplished using a recycling chiral HPLC,...
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MDPI AG
2014-03-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/19/3/2829 |
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| author | Masashi Hasegawa Seiya Iwata Yasuto Sone Junta Endo Hideyo Matsuzawa Yasuhiro Mazaki |
| author_facet | Masashi Hasegawa Seiya Iwata Yasuto Sone Junta Endo Hideyo Matsuzawa Yasuhiro Mazaki |
| author_sort | Masashi Hasegawa |
| collection | DOAJ |
| description | Dissymmetric 1,3-diphenylallene derivative 3 connected with 4,5-bis(methyl-thio)tetrathiafulvalenyl and 1-pyrenyl substituents was prepared and characterized. The molecular structure was determined by X-ray crystallographic analysis. Optical resolution was accomplished using a recycling chiral HPLC, and its chiroptical properties were examined with optical rotation and electronic circular dichroism (ECD) spectra. The title compound underwent photoracemization under daylight. This behavior was investigated in various solvents and compared with that of 1,3-bis(tetrathiafulvalenyl)allene (bis-TTF-allene) derivative 2. The first-order rate plot of the intensity of the ECD spectra at a given time interval gave the rate of racemization. Mild racemization was observed in polar solvents, whereas a relatively fast rate was obtained in less polar solvents. In addition, the TTF groups of the allene also accelerate the racemization rate. These results suggest that the racemization mechanism occurs via a non-polar diradical structure. |
| first_indexed | 2024-04-13T20:29:50Z |
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| language | English |
| last_indexed | 2024-04-13T20:29:50Z |
| publishDate | 2014-03-01 |
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| series | Molecules |
| spelling | doaj.art-cd4dbea2431e47759a38986027455c192022-12-22T02:31:13ZengMDPI AGMolecules1420-30492014-03-011932829284110.3390/molecules19032829molecules19032829Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in TetrathiafulvalenylalleneMasashi Hasegawa0Seiya Iwata1Yasuto Sone2Junta Endo3Hideyo Matsuzawa4Yasuhiro Mazaki5Department of Chemistry, School of Science, Kitasato University, Sagamihara, Kanagawa 252-0373, JapanDepartment of Chemistry, School of Science, Kitasato University, Sagamihara, Kanagawa 252-0373, JapanDepartment of Chemistry, School of Science, Kitasato University, Sagamihara, Kanagawa 252-0373, JapanDepartment of Chemistry, School of Science, Kitasato University, Sagamihara, Kanagawa 252-0373, JapanDepartment of Chemistry, School of Science, Kitasato University, Sagamihara, Kanagawa 252-0373, JapanDepartment of Chemistry, School of Science, Kitasato University, Sagamihara, Kanagawa 252-0373, JapanDissymmetric 1,3-diphenylallene derivative 3 connected with 4,5-bis(methyl-thio)tetrathiafulvalenyl and 1-pyrenyl substituents was prepared and characterized. The molecular structure was determined by X-ray crystallographic analysis. Optical resolution was accomplished using a recycling chiral HPLC, and its chiroptical properties were examined with optical rotation and electronic circular dichroism (ECD) spectra. The title compound underwent photoracemization under daylight. This behavior was investigated in various solvents and compared with that of 1,3-bis(tetrathiafulvalenyl)allene (bis-TTF-allene) derivative 2. The first-order rate plot of the intensity of the ECD spectra at a given time interval gave the rate of racemization. Mild racemization was observed in polar solvents, whereas a relatively fast rate was obtained in less polar solvents. In addition, the TTF groups of the allene also accelerate the racemization rate. These results suggest that the racemization mechanism occurs via a non-polar diradical structure.http://www.mdpi.com/1420-3049/19/3/2829axis chiralityallenetetrathiafulvaleneelectronic circular dichroismracemization |
| spellingShingle | Masashi Hasegawa Seiya Iwata Yasuto Sone Junta Endo Hideyo Matsuzawa Yasuhiro Mazaki Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in Tetrathiafulvalenylallene Molecules axis chirality allene tetrathiafulvalene electronic circular dichroism racemization |
| title | Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in Tetrathiafulvalenylallene |
| title_full | Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in Tetrathiafulvalenylallene |
| title_fullStr | Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in Tetrathiafulvalenylallene |
| title_full_unstemmed | Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in Tetrathiafulvalenylallene |
| title_short | Chiroptical Properties and the Racemization of Pyrene and Tetrathiafulvalene-Substituted Allene: Substitution and Solvent Effects on Racemization in Tetrathiafulvalenylallene |
| title_sort | chiroptical properties and the racemization of pyrene and tetrathiafulvalene substituted allene substitution and solvent effects on racemization in tetrathiafulvalenylallene |
| topic | axis chirality allene tetrathiafulvalene electronic circular dichroism racemization |
| url | http://www.mdpi.com/1420-3049/19/3/2829 |
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