Tautomerism in 8-(phenyldiazenyl)quinolin-5-ol: An attempt for pH activated rotary switch
Abstract
The tautomerism of 8-(phenyldiazenyl)quinolin-5-ol has been studied by a combination of theoretical (DFT calculations) and experimental (UV-Vis and NMR) methods. The detailed study of neutral molecules has shown that the hydrazone tautomeric form, stabilized by an intramolecular N-HMIDLINE HORIZONTAL ELLIPSISN hydrogen bond, is solely present in most of the solvents. In strong proton acceptor solvents, besides the dominant hydrazone form, the deprotonated form also appears. Solvent effects on the absorption maxima of the hydrazone form are interpreted by the linear solvation energy relationship concept, using Kamlet-Taft and Catalan models. Upon deprotonation, a substantial structural transformation is observed in the studied compound leading to a slow rotation around the Cquin-N bond. The process, as monitored by 1H NMR, is strongly solvent assisted and facilitated by proton acceptor solvents. Consequently, the investigated dye could be considered as a base-activated rotary switch.
Keywords:
Quinoline / Azo dye / Tautomerism / Rotary switch / Quantum chemistry / Molecular spectroscopySource:
Dyes and Pigments, 2020, 182Publisher:
- Elsevier Sci Ltd, Oxford
Funding / projects:
- Ministry of Science, Technological Development and Innovation of the Republic of Serbia, institutional funding - 200135 (University of Belgrade, Faculty of Technology and Metallurgy) (RS-MESTD-inst-2020-200135)
- Bulgarian National Science FundNational Science Fund of Bulgaria [MolRobot DN09/10]
DOI: 10.1016/j.dyepig.2020.108628
ISSN: 0143-7208
WoS: 000564525200003
Scopus: 2-s2.0-85087773860
Institution/Community
Tehnološko-metalurški fakultetTY - JOUR AU - Lađarević, Jelena AU - Mijin, Dušan AU - Antonov, Liudmil PY - 2020 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/4380 AB - The tautomerism of 8-(phenyldiazenyl)quinolin-5-ol has been studied by a combination of theoretical (DFT calculations) and experimental (UV-Vis and NMR) methods. The detailed study of neutral molecules has shown that the hydrazone tautomeric form, stabilized by an intramolecular N-HMIDLINE HORIZONTAL ELLIPSISN hydrogen bond, is solely present in most of the solvents. In strong proton acceptor solvents, besides the dominant hydrazone form, the deprotonated form also appears. Solvent effects on the absorption maxima of the hydrazone form are interpreted by the linear solvation energy relationship concept, using Kamlet-Taft and Catalan models. Upon deprotonation, a substantial structural transformation is observed in the studied compound leading to a slow rotation around the Cquin-N bond. The process, as monitored by 1H NMR, is strongly solvent assisted and facilitated by proton acceptor solvents. Consequently, the investigated dye could be considered as a base-activated rotary switch. PB - Elsevier Sci Ltd, Oxford T2 - Dyes and Pigments T1 - Tautomerism in 8-(phenyldiazenyl)quinolin-5-ol: An attempt for pH activated rotary switch VL - 182 DO - 10.1016/j.dyepig.2020.108628 ER -
@article{ author = "Lađarević, Jelena and Mijin, Dušan and Antonov, Liudmil", year = "2020", abstract = "The tautomerism of 8-(phenyldiazenyl)quinolin-5-ol has been studied by a combination of theoretical (DFT calculations) and experimental (UV-Vis and NMR) methods. The detailed study of neutral molecules has shown that the hydrazone tautomeric form, stabilized by an intramolecular N-HMIDLINE HORIZONTAL ELLIPSISN hydrogen bond, is solely present in most of the solvents. In strong proton acceptor solvents, besides the dominant hydrazone form, the deprotonated form also appears. Solvent effects on the absorption maxima of the hydrazone form are interpreted by the linear solvation energy relationship concept, using Kamlet-Taft and Catalan models. Upon deprotonation, a substantial structural transformation is observed in the studied compound leading to a slow rotation around the Cquin-N bond. The process, as monitored by 1H NMR, is strongly solvent assisted and facilitated by proton acceptor solvents. Consequently, the investigated dye could be considered as a base-activated rotary switch.", publisher = "Elsevier Sci Ltd, Oxford", journal = "Dyes and Pigments", title = "Tautomerism in 8-(phenyldiazenyl)quinolin-5-ol: An attempt for pH activated rotary switch", volume = "182", doi = "10.1016/j.dyepig.2020.108628" }
Lađarević, J., Mijin, D.,& Antonov, L.. (2020). Tautomerism in 8-(phenyldiazenyl)quinolin-5-ol: An attempt for pH activated rotary switch. in Dyes and Pigments Elsevier Sci Ltd, Oxford., 182. https://doi.org/10.1016/j.dyepig.2020.108628
Lađarević J, Mijin D, Antonov L. Tautomerism in 8-(phenyldiazenyl)quinolin-5-ol: An attempt for pH activated rotary switch. in Dyes and Pigments. 2020;182. doi:10.1016/j.dyepig.2020.108628 .
Lađarević, Jelena, Mijin, Dušan, Antonov, Liudmil, "Tautomerism in 8-(phenyldiazenyl)quinolin-5-ol: An attempt for pH activated rotary switch" in Dyes and Pigments, 182 (2020), https://doi.org/10.1016/j.dyepig.2020.108628 . .