TY  - CONF
AU  - Milovanović, Milan R.
AU  - Dherbassy, Quentin
AU  - Wencel-Delord, Joanna
AU  - Colobert, Françoise
AU  - Zarić, Snežana D.
AU  - Djukic, Jean-Pierre
PY  - 2020
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6357
AB  - HFIP, i.e. 1,1,1,3,3,3-hexafluoropropan-2-ol, was found to be an exceptional medium,[1] either as solvent or co-solvent, that allows many reactions to occur.[2-5] However, the exact role and mode of action of HFIP in various chemical transformations still remains elusive. Despite many reports dealing with water/HFIP complexes, little has been published on other molecular complexes of HFIP as well as on thermochemistry of the formation of such complexes.[6]
Within this study the affinity of a series of eight different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) to HFIP (as Lewis acid) is investigated 
experimentally by Isothermal Titration Calorimetry (ITC) and theoretically using static DFT-D calculations. Measured ITC association enthalpy values ΔHaITC spanned -9.3 kcal/mol - -14
kcal/mol. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems - ΔHa values ranging -8.5 – -12.7 kcal/mol. In general, most of interaction energy is due to the hydrogen bonding and not due to formation of significantly strong halogen bonds. An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIPbase complexation, which main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic miscrostructuration of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.
C3  - The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020
T1  - Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution
SP  - 161
EP  - 161
UR  - https://hdl.handle.net/21.15107/rcub_cherry_6357
ER  - 

@conference{
author = "Milovanović, Milan R. and Dherbassy, Quentin and Wencel-Delord, Joanna and Colobert, Françoise and Zarić, Snežana D. and Djukic, Jean-Pierre",
year = "2020",
abstract = "HFIP, i.e. 1,1,1,3,3,3-hexafluoropropan-2-ol, was found to be an exceptional medium,[1] either as solvent or co-solvent, that allows many reactions to occur.[2-5] However, the exact role and mode of action of HFIP in various chemical transformations still remains elusive. Despite many reports dealing with water/HFIP complexes, little has been published on other molecular complexes of HFIP as well as on thermochemistry of the formation of such complexes.[6]
Within this study the affinity of a series of eight different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) to HFIP (as Lewis acid) is investigated 
experimentally by Isothermal Titration Calorimetry (ITC) and theoretically using static DFT-D calculations. Measured ITC association enthalpy values ΔHaITC spanned -9.3 kcal/mol - -14
kcal/mol. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems - ΔHa values ranging -8.5 – -12.7 kcal/mol. In general, most of interaction energy is due to the hydrogen bonding and not due to formation of significantly strong halogen bonds. An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIPbase complexation, which main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic miscrostructuration of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.",
journal = "The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020",
title = "Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution",
pages = "161-161",
url = "https://hdl.handle.net/21.15107/rcub_cherry_6357"
}

Milovanović, M. R., Dherbassy, Q., Wencel-Delord, J., Colobert, F., Zarić, S. D.,& Djukic, J.. (2020). Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution. in The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020, 161-161.
https://hdl.handle.net/21.15107/rcub_cherry_6357

Milovanović MR, Dherbassy Q, Wencel-Delord J, Colobert F, Zarić SD, Djukic J. Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution. in The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020. 2020;:161-161.
https://hdl.handle.net/21.15107/rcub_cherry_6357 .

Milovanović, Milan R., Dherbassy, Quentin, Wencel-Delord, Joanna, Colobert, Françoise, Zarić, Snežana D., Djukic, Jean-Pierre, "Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution" in The 4th International Symposium on Halogen Bonding (ISXB4), Stellenbosch University, South Africa, 2-5 November 2020 (2020):161-161,
https://hdl.handle.net/21.15107/rcub_cherry_6357 .

TY  - CONF
AU  - Milovanović, Milan R.
AU  - Djukic, Jean-Pierre
AU  - Zarić, Snežana D.
PY  - 2019
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6362
AB  - The understanding of certain, still unknown, aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for dispersion. These methods allow accounting for, in a physically relevant way, the effects of dispersion at medium and long distance [1]. For the further assessing the accuracy of static DFT-D calculations the providing of referential experimental data was found to be essential. It has been shown that Isothermal titration calorimetry (ITC) techniques can provide reliable thermodynamic parameters of reaction (enthalpy ΔHr, Gibbs free energy ΔGr and entropy ΔSr) [2], while some recent studies showed good agreement between experimental and theoretical results [2].
The study presented here sheds some light on the thermochemistry of reactions in solution by preforming ITC experiments in chlorobenzene and static DFT-D calculations. The study points out that, in cases where solvent molecules can interact significantly with molecules of reactants, an accounting for the explicit solvation is of crucial importance for agreement between experiment and theory. The results of various kinds of organometallic reactions will be presented in some details.
PB  - Belgrade : Serbian Chemical Society
C3  - 7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019
T1  - Thermochemistry of organometallic reactions in solution: joint ITC and DFT study
UR  - https://hdl.handle.net/21.15107/rcub_cherry_6362
ER  - 

@conference{
author = "Milovanović, Milan R. and Djukic, Jean-Pierre and Zarić, Snežana D.",
year = "2019",
abstract = "The understanding of certain, still unknown, aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for dispersion. These methods allow accounting for, in a physically relevant way, the effects of dispersion at medium and long distance [1]. For the further assessing the accuracy of static DFT-D calculations the providing of referential experimental data was found to be essential. It has been shown that Isothermal titration calorimetry (ITC) techniques can provide reliable thermodynamic parameters of reaction (enthalpy ΔHr, Gibbs free energy ΔGr and entropy ΔSr) [2], while some recent studies showed good agreement between experimental and theoretical results [2].
The study presented here sheds some light on the thermochemistry of reactions in solution by preforming ITC experiments in chlorobenzene and static DFT-D calculations. The study points out that, in cases where solvent molecules can interact significantly with molecules of reactants, an accounting for the explicit solvation is of crucial importance for agreement between experiment and theory. The results of various kinds of organometallic reactions will be presented in some details.",
publisher = "Belgrade : Serbian Chemical Society",
journal = "7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019",
title = "Thermochemistry of organometallic reactions in solution: joint ITC and DFT study",
url = "https://hdl.handle.net/21.15107/rcub_cherry_6362"
}

Milovanović, M. R., Djukic, J.,& Zarić, S. D.. (2019). Thermochemistry of organometallic reactions in solution: joint ITC and DFT study. in 7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019
Belgrade : Serbian Chemical Society..
https://hdl.handle.net/21.15107/rcub_cherry_6362

Milovanović MR, Djukic J, Zarić SD. Thermochemistry of organometallic reactions in solution: joint ITC and DFT study. in 7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019. 2019;.
https://hdl.handle.net/21.15107/rcub_cherry_6362 .

Milovanović, Milan R., Djukic, Jean-Pierre, Zarić, Snežana D., "Thermochemistry of organometallic reactions in solution: joint ITC and DFT study" in 7th Conference of the Young Chemists of Serbia, Book of Abstracts, Belgrade, 2nd November 2019 (2019),
https://hdl.handle.net/21.15107/rcub_cherry_6362 .

TY  - JOUR
AU  - Milovanović, Milan R.
AU  - Dohm, Sebastian
AU  - Hansen, Andreas
AU  - Djukic, Jean-Pierre
AU  - Zarić, Snežana D.
AU  - Grimme, Stefan
PY  - 2017
UR  - https://akcongress.com/jtacc
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6364
AB  - The London forces [1–3], or dispersion, are omnipresent in the nature. It constitutes an important part of the energy contribution to the stabilization of the tertiary structure of peptides, other natural polymers and the spontaneous coalescence of atomic aggregates or apolar molecules. The specifi city of the force of London is that it acts at long distances and it is always attractive, and it is therefore effective intramolecularly and determines in many situations the conformational behaviour of organic molecules and organometallics as well. It plays an essential role in chiral recognition and discrimination processes.
The understanding of certain still unknown aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for Dispersion. These allow to account for in a physically relevant way the effects of dispersion at medium and long distance [4]. For the further assessing the accuracy of static DFT-D calculations providing a referential of experimental data was found essential.
It has been shown that ITC techniques can provide reliable reaction enthalpy ΔHr, Gibbs free energy of reaction ΔGr and reaction entropy ΔSr as well [5]. Some recent studies showed good agreement between experimental and theoretical results [6–8]. This study will shed some light on the thermochemistry of the reactions in solution by preforming ITC experiments in chlorobenzene, from one side, and static DFT-D calculations at different levels of theory, from another side (Fig. 1). By comparison of obtained results one could conclude on the
excellent agreement between experimental and theoretical data, which could be promising for the further development and application of static DFT-D computational methods. As examples, the results of various organometallic reactions will be presented in some details [9].
T2  - 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary
T1  - Benchmarking to DFT-d calculations by ITC experimental data
UR  - https://hdl.handle.net/21.15107/rcub_cherry_6364
ER  - 

@article{
author = "Milovanović, Milan R. and Dohm, Sebastian and Hansen, Andreas and Djukic, Jean-Pierre and Zarić, Snežana D. and Grimme, Stefan",
year = "2017",
abstract = "The London forces [1–3], or dispersion, are omnipresent in the nature. It constitutes an important part of the energy contribution to the stabilization of the tertiary structure of peptides, other natural polymers and the spontaneous coalescence of atomic aggregates or apolar molecules. The specifi city of the force of London is that it acts at long distances and it is always attractive, and it is therefore effective intramolecularly and determines in many situations the conformational behaviour of organic molecules and organometallics as well. It plays an essential role in chiral recognition and discrimination processes.
The understanding of certain still unknown aspects of the chemical bond is made possible by new theoretical tools, particularly static DFT-D or DFT methods corrected for Dispersion. These allow to account for in a physically relevant way the effects of dispersion at medium and long distance [4]. For the further assessing the accuracy of static DFT-D calculations providing a referential of experimental data was found essential.
It has been shown that ITC techniques can provide reliable reaction enthalpy ΔHr, Gibbs free energy of reaction ΔGr and reaction entropy ΔSr as well [5]. Some recent studies showed good agreement between experimental and theoretical results [6–8]. This study will shed some light on the thermochemistry of the reactions in solution by preforming ITC experiments in chlorobenzene, from one side, and static DFT-D calculations at different levels of theory, from another side (Fig. 1). By comparison of obtained results one could conclude on the
excellent agreement between experimental and theoretical data, which could be promising for the further development and application of static DFT-D computational methods. As examples, the results of various organometallic reactions will be presented in some details [9].",
journal = "1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary",
title = "Benchmarking to DFT-d calculations by ITC experimental data",
url = "https://hdl.handle.net/21.15107/rcub_cherry_6364"
}

Milovanović, M. R., Dohm, S., Hansen, A., Djukic, J., Zarić, S. D.,& Grimme, S.. (2017). Benchmarking to DFT-d calculations by ITC experimental data. in 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary.
https://hdl.handle.net/21.15107/rcub_cherry_6364

Milovanović MR, Dohm S, Hansen A, Djukic J, Zarić SD, Grimme S. Benchmarking to DFT-d calculations by ITC experimental data. in 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary. 2017;.
https://hdl.handle.net/21.15107/rcub_cherry_6364 .

Milovanović, Milan R., Dohm, Sebastian, Hansen, Andreas, Djukic, Jean-Pierre, Zarić, Snežana D., Grimme, Stefan, "Benchmarking to DFT-d calculations by ITC experimental data" in 1st Journal of Thermal Analysis and Caliometry Conference and 6th V4 (Joint Chech-Hungarian-Polish-Slovakian) Thermoanalytical Conference, Book of Abstracts, June 6-9, 2017, Budapest, Hungary (2017),
https://hdl.handle.net/21.15107/rcub_cherry_6364 .