Assessing the potential of para-donor and para-acceptor substituted 5-benzylidenebarbituric acid derivatives as push–pull electronic systems: Experimental and quantum chemical study
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2021
Authors
Stojiljković, Ivana N.Rančić, Milica

Marinković, Aleksandar
Cvijetić, Ilija

Milčić, Miloš K.

Article (Published version)

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Electronic interactions in donor-π-linker-acceptor systems with barbituric acid as an electron acceptor and possible electron donor were investigated to screen promising candidates with a push–pull character based on experimental and quantum chemical studies. The tautomeric properties of 5-benzylidenebarbituric acid derivatives were studied with NMR spectra, spectrophotometric determination of the pKa values, and quantum chemical calculations. Linear solvation energy relationships (LSER) and linear free energy relationships (LFER) were applied to the spectral data - UV frequencies and 13C NMR chemical shifts. The experimental studies of the nature of the ground and excited state of investigated compounds were successfully interpreted using a computational chemistry approach including ab initio MP2 geometry optimization and time-dependent DFT calculations of excited states. Quantification of the push–pull character of barbituric acid derivatives was performed by the 13CNMR chemical shif...t differences, Mayer π bond order analysis, hole-electron distribution analysis, and calculations of intramolecular charge transfer (ICT) indices. The results obtained show, that when coupled with a strong electron-donor, barbituric acid can act as the electron-acceptor in push–pull systems, and when coupled with a strong electron-acceptor, barbituric acid can act as the weak electron-donor.
Keywords:
Barbituric acid derivatives / Hole-electron distribution analysis / ICT process / LFER analysis / Push–pull systemsSource:
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2021, 253, 119576-Publisher:
- Elsevier
Funding / projects:
Note:
- Supplementary material: https://cherry.chem.bg.ac.rs/handle/123456789/4421
Related info:
- Version of
https://doi.org/10.1016/j.saa.2021.119576 - Referenced by
https://cherry.chem.bg.ac.rs/handle/123456789/4421
DOI: 10.1016/j.saa.2021.119576
ISSN: 1386-1425
WoS: 000635167000012
Scopus: 2-s2.0-85101104882
URI
https://www.sciencedirect.com/science/article/pii/S1386142521001529https://cherry.chem.bg.ac.rs/handle/123456789/4420
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Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Stojiljković, Ivana N. AU - Rančić, Milica AU - Marinković, Aleksandar AU - Cvijetić, Ilija AU - Milčić, Miloš K. PY - 2021 UR - https://www.sciencedirect.com/science/article/pii/S1386142521001529 UR - https://cherry.chem.bg.ac.rs/handle/123456789/4420 AB - Electronic interactions in donor-π-linker-acceptor systems with barbituric acid as an electron acceptor and possible electron donor were investigated to screen promising candidates with a push–pull character based on experimental and quantum chemical studies. The tautomeric properties of 5-benzylidenebarbituric acid derivatives were studied with NMR spectra, spectrophotometric determination of the pKa values, and quantum chemical calculations. Linear solvation energy relationships (LSER) and linear free energy relationships (LFER) were applied to the spectral data - UV frequencies and 13C NMR chemical shifts. The experimental studies of the nature of the ground and excited state of investigated compounds were successfully interpreted using a computational chemistry approach including ab initio MP2 geometry optimization and time-dependent DFT calculations of excited states. Quantification of the push–pull character of barbituric acid derivatives was performed by the 13CNMR chemical shift differences, Mayer π bond order analysis, hole-electron distribution analysis, and calculations of intramolecular charge transfer (ICT) indices. The results obtained show, that when coupled with a strong electron-donor, barbituric acid can act as the electron-acceptor in push–pull systems, and when coupled with a strong electron-acceptor, barbituric acid can act as the weak electron-donor. PB - Elsevier T2 - Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy T2 - Spectrochimica Acta Part A: Molecular and Biomolecular SpectroscopySpectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy T1 - Assessing the potential of para-donor and para-acceptor substituted 5-benzylidenebarbituric acid derivatives as push–pull electronic systems: Experimental and quantum chemical study VL - 253 SP - 119576 DO - 10.1016/j.saa.2021.119576 ER -
@article{ author = "Stojiljković, Ivana N. and Rančić, Milica and Marinković, Aleksandar and Cvijetić, Ilija and Milčić, Miloš K.", year = "2021", abstract = "Electronic interactions in donor-π-linker-acceptor systems with barbituric acid as an electron acceptor and possible electron donor were investigated to screen promising candidates with a push–pull character based on experimental and quantum chemical studies. The tautomeric properties of 5-benzylidenebarbituric acid derivatives were studied with NMR spectra, spectrophotometric determination of the pKa values, and quantum chemical calculations. Linear solvation energy relationships (LSER) and linear free energy relationships (LFER) were applied to the spectral data - UV frequencies and 13C NMR chemical shifts. The experimental studies of the nature of the ground and excited state of investigated compounds were successfully interpreted using a computational chemistry approach including ab initio MP2 geometry optimization and time-dependent DFT calculations of excited states. Quantification of the push–pull character of barbituric acid derivatives was performed by the 13CNMR chemical shift differences, Mayer π bond order analysis, hole-electron distribution analysis, and calculations of intramolecular charge transfer (ICT) indices. The results obtained show, that when coupled with a strong electron-donor, barbituric acid can act as the electron-acceptor in push–pull systems, and when coupled with a strong electron-acceptor, barbituric acid can act as the weak electron-donor.", publisher = "Elsevier", journal = "Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Spectrochimica Acta Part A: Molecular and Biomolecular SpectroscopySpectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy", title = "Assessing the potential of para-donor and para-acceptor substituted 5-benzylidenebarbituric acid derivatives as push–pull electronic systems: Experimental and quantum chemical study", volume = "253", pages = "119576", doi = "10.1016/j.saa.2021.119576" }
Stojiljković, I. N., Rančić, M., Marinković, A., Cvijetić, I.,& Milčić, M. K.. (2021). Assessing the potential of para-donor and para-acceptor substituted 5-benzylidenebarbituric acid derivatives as push–pull electronic systems: Experimental and quantum chemical study. in Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy Elsevier., 253, 119576. https://doi.org/10.1016/j.saa.2021.119576
Stojiljković IN, Rančić M, Marinković A, Cvijetić I, Milčić MK. Assessing the potential of para-donor and para-acceptor substituted 5-benzylidenebarbituric acid derivatives as push–pull electronic systems: Experimental and quantum chemical study. in Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2021;253:119576. doi:10.1016/j.saa.2021.119576 .
Stojiljković, Ivana N., Rančić, Milica, Marinković, Aleksandar, Cvijetić, Ilija, Milčić, Miloš K., "Assessing the potential of para-donor and para-acceptor substituted 5-benzylidenebarbituric acid derivatives as push–pull electronic systems: Experimental and quantum chemical study" in Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 253 (2021):119576, https://doi.org/10.1016/j.saa.2021.119576 . .