Solvent and substituent effect on intramolecular charge transfer in 5-arylidene-3-substituted-2,4-thiazolidinediones: Experimental and theoretical study

2016
Authors
Rančić, Milica
Stojiljković, Ivana N.
Milošević, Milena D.
Prlainović, Nevena Z.
Jovanović, Maja

Milčić, Miloš K.

Marinković, Aleksandar
Article (Published version)
Metadata
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The substituent and solvent effect on intramolecular charge transfer (ICT) in 5-arylidene-3-methyl-2,4-thiazolidinediones (series 1) and 5-arylidene-3-phenyl-2,4-thiazolidinediones (series 2) was studied by using experimental and theoretical methodology. The effect of specific and non-specific solvent-solute interactions on the UV-vis absorption maxima shifts was evaluated by using the Kamlet-Taft and Catalán solvent parameter sets. Linear free energy relationships (LFERs) have been applied to the UV-vis and 13C NMR data by using SSP (single substituent parameter) and DSP (dual substituent parameters). Comparative LFER analysis of 10 styrenic series was performed in order to distinguish contribution of structural and electronic substituent effect on extent of π-polarization in a side chain (vinyl) group. Furthermore, the experimental findings were interpreted with the aid of ab initio MP2 and time-dependent density functional (TD-DFT) methods. TD-DFT calculations are performed to quant...ify the efficiency of intramolecular charge transfer (ICT) allowing us to define the charge-transfer distance (DCT), amount of transferred charge (QCT), and difference of dipole moments between the ground and excited states (μCT). It was found that both substituents and solvents influence electron density shift, i.e. extent of conjugation, and affect intramolecular charge transfer character in the course of excitation. © 2016 The Authors.
Keywords:
LFER / LSER / Quantum chemical calculation / Solvatochromism / Substituent effectSource:
Arabian Journal of Chemistry, 2016Funding / projects:
- Study of the Synthesis, Structure and Activity of Natural and Synthetic Organic Compounds (RS-172013)
Note:
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3613
DOI: 10.1016/j.arabjc.2016.12.013
ISSN: 1878-5352
WoS: 000504900300310
Scopus: 2-s2.0-85009209267
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Hemijski fakultetTY - JOUR AU - Rančić, Milica AU - Stojiljković, Ivana N. AU - Milošević, Milena D. AU - Prlainović, Nevena Z. AU - Jovanović, Maja AU - Milčić, Miloš K. AU - Marinković, Aleksandar PY - 2016 UR - https://cherry.chem.bg.ac.rs/handle/123456789/305 AB - The substituent and solvent effect on intramolecular charge transfer (ICT) in 5-arylidene-3-methyl-2,4-thiazolidinediones (series 1) and 5-arylidene-3-phenyl-2,4-thiazolidinediones (series 2) was studied by using experimental and theoretical methodology. The effect of specific and non-specific solvent-solute interactions on the UV-vis absorption maxima shifts was evaluated by using the Kamlet-Taft and Catalán solvent parameter sets. Linear free energy relationships (LFERs) have been applied to the UV-vis and 13C NMR data by using SSP (single substituent parameter) and DSP (dual substituent parameters). Comparative LFER analysis of 10 styrenic series was performed in order to distinguish contribution of structural and electronic substituent effect on extent of π-polarization in a side chain (vinyl) group. Furthermore, the experimental findings were interpreted with the aid of ab initio MP2 and time-dependent density functional (TD-DFT) methods. TD-DFT calculations are performed to quantify the efficiency of intramolecular charge transfer (ICT) allowing us to define the charge-transfer distance (DCT), amount of transferred charge (QCT), and difference of dipole moments between the ground and excited states (μCT). It was found that both substituents and solvents influence electron density shift, i.e. extent of conjugation, and affect intramolecular charge transfer character in the course of excitation. © 2016 The Authors. T2 - Arabian Journal of Chemistry T1 - Solvent and substituent effect on intramolecular charge transfer in 5-arylidene-3-substituted-2,4-thiazolidinediones: Experimental and theoretical study DO - 10.1016/j.arabjc.2016.12.013 UR - Kon_1269 ER -
@article{ author = "Rančić, Milica and Stojiljković, Ivana N. and Milošević, Milena D. and Prlainović, Nevena Z. and Jovanović, Maja and Milčić, Miloš K. and Marinković, Aleksandar", year = "2016", abstract = "The substituent and solvent effect on intramolecular charge transfer (ICT) in 5-arylidene-3-methyl-2,4-thiazolidinediones (series 1) and 5-arylidene-3-phenyl-2,4-thiazolidinediones (series 2) was studied by using experimental and theoretical methodology. The effect of specific and non-specific solvent-solute interactions on the UV-vis absorption maxima shifts was evaluated by using the Kamlet-Taft and Catalán solvent parameter sets. Linear free energy relationships (LFERs) have been applied to the UV-vis and 13C NMR data by using SSP (single substituent parameter) and DSP (dual substituent parameters). Comparative LFER analysis of 10 styrenic series was performed in order to distinguish contribution of structural and electronic substituent effect on extent of π-polarization in a side chain (vinyl) group. Furthermore, the experimental findings were interpreted with the aid of ab initio MP2 and time-dependent density functional (TD-DFT) methods. TD-DFT calculations are performed to quantify the efficiency of intramolecular charge transfer (ICT) allowing us to define the charge-transfer distance (DCT), amount of transferred charge (QCT), and difference of dipole moments between the ground and excited states (μCT). It was found that both substituents and solvents influence electron density shift, i.e. extent of conjugation, and affect intramolecular charge transfer character in the course of excitation. © 2016 The Authors.", journal = "Arabian Journal of Chemistry", title = "Solvent and substituent effect on intramolecular charge transfer in 5-arylidene-3-substituted-2,4-thiazolidinediones: Experimental and theoretical study", doi = "10.1016/j.arabjc.2016.12.013", url = "Kon_1269" }
Rančić, M., Stojiljković, I. N., Milošević, M. D., Prlainović, N. Z., Jovanović, M., Milčić, M. K.,& Marinković, A.. (2016). Solvent and substituent effect on intramolecular charge transfer in 5-arylidene-3-substituted-2,4-thiazolidinediones: Experimental and theoretical study. in Arabian Journal of Chemistry. https://doi.org/10.1016/j.arabjc.2016.12.013 Kon_1269
Rančić M, Stojiljković IN, Milošević MD, Prlainović NZ, Jovanović M, Milčić MK, Marinković A. Solvent and substituent effect on intramolecular charge transfer in 5-arylidene-3-substituted-2,4-thiazolidinediones: Experimental and theoretical study. in Arabian Journal of Chemistry. 2016;. doi:10.1016/j.arabjc.2016.12.013 Kon_1269 .
Rančić, Milica, Stojiljković, Ivana N., Milošević, Milena D., Prlainović, Nevena Z., Jovanović, Maja, Milčić, Miloš K., Marinković, Aleksandar, "Solvent and substituent effect on intramolecular charge transfer in 5-arylidene-3-substituted-2,4-thiazolidinediones: Experimental and theoretical study" in Arabian Journal of Chemistry (2016), https://doi.org/10.1016/j.arabjc.2016.12.013 ., Kon_1269 .