Synthesis and Computational Study of New 1H-pyrrol-2-carboxaldehyde [(1E)-(2-hydroxy naphtyl) methylene]hydrazone / Boucherabine, djihed  

Public ISBD Titre : Synthesis and Computational Study of New 1H-pyrrol-2-carboxaldehyde [(1E)-(2-hydroxy naphtyl) methylene]hydrazone Type de document : texte imprimé Auteurs : Boucherabine, djihed ; Douniazed HANNACHI, Directeur de thèse Editeur : Setif:UFA Année de publication : 2017 Importance : 1vol. (66f.) Format : 30cm. Catégories : Thèses & Mémoires:Chimie Mots-clés : syntesis,computational,1H-PYRROL-2CARBOXLDEHYDE,methylene,hydrazone Résumé : Conclusion Quantum chemical calculation results presented above address several key issues in understanding the structure, IR vibration, UV-vis spectra, nonlinear optical response, reactivity and protonation mechanism of the new Azine compounds. On the basis of our studies the following conclusion can be drawn -The optimized geometrie of 1H-pyrrol-2-carboxaldehyde [(1E)-(2-hydroxy naphtyl) methylene]hydrazone with M05-2X functional is in good agreement with the experimental values -Comparing the simulated spectra with experimental one, we can notice that pure B3LYP functional can better reproduce the IR and UV–vis spectra than the PBEEBE, CAM-B3YP and M05-2X, but empirical dispersion corrections B3LYP-D3 and B3LYP-BJ has better performance than B3LYP. -The dispersion interactions are largest for Azine-TS and smallest for Azine and Azine-P. These results reveal that the strengths of dispersion interactions are sensitive to interaction between H...O and H...N fragments. -The DFT-D3 dispersion corrections to the thermodynamic energies and kinetic energies are smaller than the corresponding DFT-BJ dispersion corrections. - On the other hand and for the first time, our results demonstrate that: That the polarizabilities and hyperpolarizabilities in solvent phase increase with the raising of the dipole moment () of the solvated organic compounds and a large correlation between the (β0 and μ) is obtained. There is no clear correlation between the dielectric constant of a solvent and its dipolar moment and the first hyperpolarizability of the title compounds. Q 58 The rate constants on the protonation process of Azine in solvent phase have a proportional relation with the dielectric constant of the solvent. On the other hand, in the backward protonation process the rate constant decrease with the increasing of the dielectric constant of the solvent. Our theoretical results demonstrated that, the deprotonation of hydrogen atom (H2) from the strong cage (H2-O10-C3-C18-C19 and N21) is necessary condition for the complexation the Azine with metal ion. We conclude that the title compounds is an attractive object for future studies of nonlinear optical properties. Note de contenu : Contents Acknowledgements iii List of figures iv List of tables vi General introduction 1 Reference 2 Chapter 1: Density Functional Theory I.1.1.The introduction of DFT into chemistry 3 I.1.2.The DFT work in the coordination chemistry lab 4 I.1.2.1.Capabilities of DFT 4 I.2.Basics of the theory of DFT 4 I.3.DFT tools available (Exchange Correlation Functionals) 5 I.3.1. Local density approximation: 7 I.3.2.Generalized-gradient approximation (GGA) : 7 I.3.3.Meta-GGA DFs : 8 I.3.4.Hybrid DFs : 9 I.3.5.Double hybrid DFs 10 I.4.General comments on the most popular density functionals 11 I.5.Jacob’s ladder 12 I.6.Conclusion 14 Reference 15 Chapter 2: results and discussions II.1. Introduction 17 II.2. Computational method 18 II.2.1. Van der Waals correction 13 II.3. Experimental study 13 II.3.1. The principle 19 II.3.2. General procedure for preparation of Azine 20 II.3.3. The mechanism 21 II.3.4. Spectroscopy 22 II.3.5. Crystal structure determination 24 II.4. Computational study 24 II.4.1. Molecular structures 25 II.4.2. Vibrational modes 26 II.4.2.1. Error analysis of different vibrational calculations 27 II.4.3. Reactivity 28 II.4.3.1. Fukui indices for protonation site identification 29 II.4.3.2. Global reactivity indices 31 II.4.3.3. Local reactivity indices 31 II.4.4. Tautomerization reaction 32 II.4.4.1. H-bond geometries 32 II.4.4.2. Energy barriers and the reaction energies 36 II.4.4.3. The effect of empirical dispersion corrections 37 II.4.5. Nonlinear optical properties 38 ii II.4.5.1. Polarizability and first hyperpolarizability 40 II.4.5.2. Effect of solvent 45 II.4.5.3. The effect of empirical dispersion corrections 46 II.4.6. TD-DFT 51 II.4.7. Molecular electrostatic potential 53 References 54 conclusion 57 Supplementary-data 59 Côte titre : MACH/0048 En ligne : https://drive.google.com/file/d/1MvzzlJ6ec7_qcODQ3gdxypWLWfRhU3tR/view?usp=shari [...] Format de la ressource électronique : pdf Synthesis and Computational Study of New 1H-pyrrol-2-carboxaldehyde [(1E)-(2-hydroxy naphtyl) methylene]hydrazone [texte imprimé] / Boucherabine, djihed ; Douniazed HANNACHI, Directeur de thèse . - [S.l.] : Setif:UFA, 2017 . - 1vol. (66f.) ; 30cm. Catégories : Thèses & Mémoires:Chimie Mots-clés : syntesis,computational,1H-PYRROL-2CARBOXLDEHYDE,methylene,hydrazone Résumé : Conclusion Quantum chemical calculation results presented above address several key issues in understanding the structure, IR vibration, UV-vis spectra, nonlinear optical response, reactivity and protonation mechanism of the new Azine compounds. On the basis of our studies the following conclusion can be drawn -The optimized geometrie of 1H-pyrrol-2-carboxaldehyde [(1E)-(2-hydroxy naphtyl) methylene]hydrazone with M05-2X functional is in good agreement with the experimental values -Comparing the simulated spectra with experimental one, we can notice that pure B3LYP functional can better reproduce the IR and UV–vis spectra than the PBEEBE, CAM-B3YP and M05-2X, but empirical dispersion corrections B3LYP-D3 and B3LYP-BJ has better performance than B3LYP. -The dispersion interactions are largest for Azine-TS and smallest for Azine and Azine-P. These results reveal that the strengths of dispersion interactions are sensitive to interaction between H...O and H...N fragments. -The DFT-D3 dispersion corrections to the thermodynamic energies and kinetic energies are smaller than the corresponding DFT-BJ dispersion corrections. - On the other hand and for the first time, our results demonstrate that: That the polarizabilities and hyperpolarizabilities in solvent phase increase with the raising of the dipole moment () of the solvated organic compounds and a large correlation between the (β0 and μ) is obtained. There is no clear correlation between the dielectric constant of a solvent and its dipolar moment and the first hyperpolarizability of the title compounds. Q 58 The rate constants on the protonation process of Azine in solvent phase have a proportional relation with the dielectric constant of the solvent. On the other hand, in the backward protonation process the rate constant decrease with the increasing of the dielectric constant of the solvent. Our theoretical results demonstrated that, the deprotonation of hydrogen atom (H2) from the strong cage (H2-O10-C3-C18-C19 and N21) is necessary condition for the complexation the Azine with metal ion. We conclude that the title compounds is an attractive object for future studies of nonlinear optical properties. Note de contenu : Contents Acknowledgements iii List of figures iv List of tables vi General introduction 1 Reference 2 Chapter 1: Density Functional Theory I.1.1.The introduction of DFT into chemistry 3 I.1.2.The DFT work in the coordination chemistry lab 4 I.1.2.1.Capabilities of DFT 4 I.2.Basics of the theory of DFT 4 I.3.DFT tools available (Exchange Correlation Functionals) 5 I.3.1. Local density approximation: 7 I.3.2.Generalized-gradient approximation (GGA) : 7 I.3.3.Meta-GGA DFs : 8 I.3.4.Hybrid DFs : 9 I.3.5.Double hybrid DFs 10 I.4.General comments on the most popular density functionals 11 I.5.Jacob’s ladder 12 I.6.Conclusion 14 Reference 15 Chapter 2: results and discussions II.1. Introduction 17 II.2. Computational method 18 II.2.1. Van der Waals correction 13 II.3. Experimental study 13 II.3.1. The principle 19 II.3.2. General procedure for preparation of Azine 20 II.3.3. The mechanism 21 II.3.4. Spectroscopy 22 II.3.5. Crystal structure determination 24 II.4. Computational study 24 II.4.1. Molecular structures 25 II.4.2. Vibrational modes 26 II.4.2.1. Error analysis of different vibrational calculations 27 II.4.3. Reactivity 28 II.4.3.1. Fukui indices for protonation site identification 29 II.4.3.2. Global reactivity indices 31 II.4.3.3. Local reactivity indices 31 II.4.4. Tautomerization reaction 32 II.4.4.1. H-bond geometries 32 II.4.4.2. Energy barriers and the reaction energies 36 II.4.4.3. The effect of empirical dispersion corrections 37 II.4.5. Nonlinear optical properties 38 ii II.4.5.1. Polarizability and first hyperpolarizability 40 II.4.5.2. Effect of solvent 45 II.4.5.3. The effect of empirical dispersion corrections 46 II.4.6. TD-DFT 51 II.4.7. Molecular electrostatic potential 53 References 54 conclusion 57 Supplementary-data 59 Côte titre : MACH/0048 En ligne : https://drive.google.com/file/d/1MvzzlJ6ec7_qcODQ3gdxypWLWfRhU3tR/view?usp=shari [...] Format de la ressource électronique : pdf

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