1,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties
1,6- and 1,7-regioisomers of diamino-substituted perylene tetracarboxylic dianhydrides (PTCDs) with different n-alkyl chain lengths (n = 6, 12 or 18) were synthesized and characterized by NMR spectroscopy and high-resolution mass spectrometry. These dyes are highly soluble in most organic solvents a...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2015-08-01
|
| Series: | Materials |
| Subjects: | |
| Online Access: | http://www.mdpi.com/1996-1944/8/8/4943 |
| _version_ | 1811209770855563264 |
|---|---|
| author | Kew-Yu Chen Che-Wei Chang Hsing-Yang Tsai |
| author_facet | Kew-Yu Chen Che-Wei Chang Hsing-Yang Tsai |
| author_sort | Kew-Yu Chen |
| collection | DOAJ |
| description | 1,6- and 1,7-regioisomers of diamino-substituted perylene tetracarboxylic dianhydrides (PTCDs) with different n-alkyl chain lengths (n = 6, 12 or 18) were synthesized and characterized by NMR spectroscopy and high-resolution mass spectrometry. These dyes are highly soluble in most organic solvents and even in nonpolar solvents, such as hexane. To the best of our knowledge, this is the first time the 1,6-diamino-substituted PTCDs (2a–2c) have been obtained in pure form. The regioisomers 1a–1c (1,7-) and 2a–2c (1,6-) exhibit significant differences in their optical characteristics. In addition to the longest wavelength absorption band at around 674 nm, 2a–2c exhibit another shoulder band at ca. 600 nm, and consequently, cover a large part of the visible region relative to those of 1a–1c. Upon excitation, 2a–2c also show larger dipole moment changes than those of 1a–1c; the dipole moments of all compounds have been estimated using Lippert–Mataga equation. Moreover, all the dyes show a unique charge transfer emission in the near-infrared region, of which the peak wavelengths exhibit strong solvatochromism. They all exhibit one irreversible one-electron oxidation and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory calculations performed on these chromophores are reported in order to rationalize their electronic structure and optical properties. |
| first_indexed | 2024-04-12T04:45:43Z |
| format | Article |
| id | doaj.art-4e4e57cf71984a67963fa2687b83cdd8 |
| institution | Directory Open Access Journal |
| issn | 1996-1944 |
| language | English |
| last_indexed | 2024-04-12T04:45:43Z |
| publishDate | 2015-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Materials |
| spelling | doaj.art-4e4e57cf71984a67963fa2687b83cdd82022-12-22T03:47:31ZengMDPI AGMaterials1996-19442015-08-01884943496010.3390/ma8084943ma80849431,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical PropertiesKew-Yu Chen0Che-Wei Chang1Hsing-Yang Tsai2Department of Chemical Engineering, Feng Chia University, Taichung 40724, TaiwanDepartment of Chemical Engineering, Feng Chia University, Taichung 40724, TaiwanDepartment of Chemical Engineering, Feng Chia University, Taichung 40724, Taiwan1,6- and 1,7-regioisomers of diamino-substituted perylene tetracarboxylic dianhydrides (PTCDs) with different n-alkyl chain lengths (n = 6, 12 or 18) were synthesized and characterized by NMR spectroscopy and high-resolution mass spectrometry. These dyes are highly soluble in most organic solvents and even in nonpolar solvents, such as hexane. To the best of our knowledge, this is the first time the 1,6-diamino-substituted PTCDs (2a–2c) have been obtained in pure form. The regioisomers 1a–1c (1,7-) and 2a–2c (1,6-) exhibit significant differences in their optical characteristics. In addition to the longest wavelength absorption band at around 674 nm, 2a–2c exhibit another shoulder band at ca. 600 nm, and consequently, cover a large part of the visible region relative to those of 1a–1c. Upon excitation, 2a–2c also show larger dipole moment changes than those of 1a–1c; the dipole moments of all compounds have been estimated using Lippert–Mataga equation. Moreover, all the dyes show a unique charge transfer emission in the near-infrared region, of which the peak wavelengths exhibit strong solvatochromism. They all exhibit one irreversible one-electron oxidation and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory calculations performed on these chromophores are reported in order to rationalize their electronic structure and optical properties.http://www.mdpi.com/1996-1944/8/8/4943diamino-substituted perylene tetracarboxylic dianhydridesintramolecular charge transfernear-infrared fluorescent dyessolvatochromismLippert–Mataga equationdensity functional theory calculations |
| spellingShingle | Kew-Yu Chen Che-Wei Chang Hsing-Yang Tsai 1,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties Materials diamino-substituted perylene tetracarboxylic dianhydrides intramolecular charge transfer near-infrared fluorescent dyes solvatochromism Lippert–Mataga equation density functional theory calculations |
| title | 1,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties |
| title_full | 1,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties |
| title_fullStr | 1,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties |
| title_full_unstemmed | 1,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties |
| title_short | 1,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties |
| title_sort | 1 6 and 1 7 regioisomers of highly soluble amino substituted perylene tetracarboxylic dianhydrides synthesis optical and electrochemical properties |
| topic | diamino-substituted perylene tetracarboxylic dianhydrides intramolecular charge transfer near-infrared fluorescent dyes solvatochromism Lippert–Mataga equation density functional theory calculations |
| url | http://www.mdpi.com/1996-1944/8/8/4943 |
| work_keys_str_mv | AT kewyuchen 16and17regioisomersofhighlysolubleaminosubstitutedperylenetetracarboxylicdianhydridessynthesisopticalandelectrochemicalproperties AT cheweichang 16and17regioisomersofhighlysolubleaminosubstitutedperylenetetracarboxylicdianhydridessynthesisopticalandelectrochemicalproperties AT hsingyangtsai 16and17regioisomersofhighlysolubleaminosubstitutedperylenetetracarboxylicdianhydridessynthesisopticalandelectrochemicalproperties |