CER - Central Repository
Institute of Chemistry, Technology and Metallurgy
    • English
    • Српски
    • Српски (Serbia)
  • English 
    • English
    • Serbian (Cyrillic)
    • Serbian (Latin)
  • Login
View Item 
  •   CER
  • IHTM
  • Radovi istraživača / Researchers' publications
  • View Item
  •   CER
  • IHTM
  • Radovi istraživača / Researchers' publications
  • View Item
JavaScript is disabled for your browser. Some features of this site may not work without it.

Spectroscopic and quantum chemical investigations of substituent effects on the azo-hydrazone tautomerism and acid-base properties of arylazo pyridone dyes

Authorized Users Only
2014
Authors
Dostanić, Jasmina
Mijin, Dušan
Ušćumlić, Gordana
Jovanović, Dušan M.
Zlatar, Matija
Lončarević, Davor
Article (Published version)
Metadata
Show full item record
Abstract
A series of 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridone dyes was synthesized and the structure of the dyes was confirmed by UV-Vis, FT-IR, H-1 NMR and C-13 NMR spectroscopic techniques. The azo-hydrazone tautomeric equilibrium was found to depend on the substituents as well as on the acidity and basicity of the media. Ionization constant, pK(a), of the dyes was determined by UV-Vis spectroscopy and correlated with the Hammett substituent constants, sigma(p) and sigma(I). The interpretation of the effect of different substituent in phenyl ring of arylazo pyridone dyes on their spectroscopic and structural properties was based on quantum chemical calculations performed by the density functional theory (DET/M06-2X) method. The DFT calculations confirmed the existence of two forms in water solution: hydrazone form in acidic and neutral media and anionic form in basic media. The different contribution of azo and hydrazone canonical forms of anionic form is observed for d...yes with electron-donating and dyes with electron-withdrawing groups. The dependence of absorption spectra and determined pK(a) values to the substituent type seems to be mostly due to azo/hydrazone canonical structure ratio in their anionic form.

Keywords:
Azo dyes / Azo-hydrazone tautomerism / Absorption spectra / pK(a) / DFT
Source:
Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 2014, 123, 37-45
Publisher:
  • Oxford : Pergamon-Elsevier Science Ltd
Funding / projects:
  • Nanostructured Functional and Composite Materials in Catalytic and Sorption Processes (RS-45001)
  • Study of the Synthesis, Structure and Activity of Natural and Synthetic Organic Compounds (RS-172013)

DOI: 10.1016/j.saa.2013.12.064

ISSN: 1386-1425

PubMed: 24388998

WoS: 000333777200007

Scopus: 2-s2.0-84891791908
[ Google Scholar ]
28
26
URI
https://cer.ihtm.bg.ac.rs/handle/123456789/1512
Collections
  • Radovi istraživača / Researchers' publications
Institution/Community
IHTM
TY  - JOUR
AU  - Dostanić, Jasmina
AU  - Mijin, Dušan
AU  - Ušćumlić, Gordana
AU  - Jovanović, Dušan M.
AU  - Zlatar, Matija
AU  - Lončarević, Davor
PY  - 2014
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/1512
AB  - A series of 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridone dyes was synthesized and the structure of the dyes was confirmed by UV-Vis, FT-IR, H-1 NMR and C-13 NMR spectroscopic techniques. The azo-hydrazone tautomeric equilibrium was found to depend on the substituents as well as on the acidity and basicity of the media. Ionization constant, pK(a), of the dyes was determined by UV-Vis spectroscopy and correlated with the Hammett substituent constants, sigma(p) and sigma(I). The interpretation of the effect of different substituent in phenyl ring of arylazo pyridone dyes on their spectroscopic and structural properties was based on quantum chemical calculations performed by the density functional theory (DET/M06-2X) method. The DFT calculations confirmed the existence of two forms in water solution: hydrazone form in acidic and neutral media and anionic form in basic media. The different contribution of azo and hydrazone canonical forms of anionic form is observed for dyes with electron-donating and dyes with electron-withdrawing groups. The dependence of absorption spectra and determined pK(a) values to the substituent type seems to be mostly due to azo/hydrazone canonical structure ratio in their anionic form.
PB  - Oxford : Pergamon-Elsevier Science Ltd
T2  - Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy
T1  - Spectroscopic and quantum chemical investigations of substituent effects on the azo-hydrazone tautomerism and acid-base properties of arylazo pyridone dyes
VL  - 123
SP  - 37
EP  - 45
DO  - 10.1016/j.saa.2013.12.064
ER  - 
@article{
author = "Dostanić, Jasmina and Mijin, Dušan and Ušćumlić, Gordana and Jovanović, Dušan M. and Zlatar, Matija and Lončarević, Davor",
year = "2014",
abstract = "A series of 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridone dyes was synthesized and the structure of the dyes was confirmed by UV-Vis, FT-IR, H-1 NMR and C-13 NMR spectroscopic techniques. The azo-hydrazone tautomeric equilibrium was found to depend on the substituents as well as on the acidity and basicity of the media. Ionization constant, pK(a), of the dyes was determined by UV-Vis spectroscopy and correlated with the Hammett substituent constants, sigma(p) and sigma(I). The interpretation of the effect of different substituent in phenyl ring of arylazo pyridone dyes on their spectroscopic and structural properties was based on quantum chemical calculations performed by the density functional theory (DET/M06-2X) method. The DFT calculations confirmed the existence of two forms in water solution: hydrazone form in acidic and neutral media and anionic form in basic media. The different contribution of azo and hydrazone canonical forms of anionic form is observed for dyes with electron-donating and dyes with electron-withdrawing groups. The dependence of absorption spectra and determined pK(a) values to the substituent type seems to be mostly due to azo/hydrazone canonical structure ratio in their anionic form.",
publisher = "Oxford : Pergamon-Elsevier Science Ltd",
journal = "Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy",
title = "Spectroscopic and quantum chemical investigations of substituent effects on the azo-hydrazone tautomerism and acid-base properties of arylazo pyridone dyes",
volume = "123",
pages = "37-45",
doi = "10.1016/j.saa.2013.12.064"
}
Dostanić, J., Mijin, D., Ušćumlić, G., Jovanović, D. M., Zlatar, M.,& Lončarević, D.. (2014). Spectroscopic and quantum chemical investigations of substituent effects on the azo-hydrazone tautomerism and acid-base properties of arylazo pyridone dyes. in Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy
Oxford : Pergamon-Elsevier Science Ltd., 123, 37-45.
https://doi.org/10.1016/j.saa.2013.12.064
Dostanić J, Mijin D, Ušćumlić G, Jovanović DM, Zlatar M, Lončarević D. Spectroscopic and quantum chemical investigations of substituent effects on the azo-hydrazone tautomerism and acid-base properties of arylazo pyridone dyes. in Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy. 2014;123:37-45.
doi:10.1016/j.saa.2013.12.064 .
Dostanić, Jasmina, Mijin, Dušan, Ušćumlić, Gordana, Jovanović, Dušan M., Zlatar, Matija, Lončarević, Davor, "Spectroscopic and quantum chemical investigations of substituent effects on the azo-hydrazone tautomerism and acid-base properties of arylazo pyridone dyes" in Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 123 (2014):37-45,
https://doi.org/10.1016/j.saa.2013.12.064 . .

DSpace software copyright © 2002-2015  DuraSpace
About CeR – Central Repository | Send Feedback

re3dataOpenAIRERCUB
 

 

All of DSpaceInstitutions/communitiesAuthorsTitlesSubjectsThis institutionAuthorsTitlesSubjects

Statistics

View Usage Statistics

DSpace software copyright © 2002-2015  DuraSpace
About CeR – Central Repository | Send Feedback

re3dataOpenAIRERCUB