Nucleophilic Regions Research Articles

Theoretical Density Functional Theory insights into the nature of chalcogen bonding between CX2 (X = S, Se, Te) and diazine from monomer to supramolecular complexes

AbstractChalcogen bonding is a noncovalent interaction, highly similar to halogen and hydrogen bonding, occurring between a chalcogen atom and a nucleophilic region. Two density functional theory (DFT) approaches B3LY‐D3 and B97‐D3 were performed on a series of complexes formed between CX2 (X = S, Se, Te) and diazine (pyridazine, pyrimidine and pyrazine). Chalcogen atoms prefer interacting with the lone pair of a nitrogen atom rather than with the π‐cloud of an aromatic ring. CTe2 and CSe2 form a stronger chalcogen bond than CS2. The electrostatic potential of CX2 (X = S, Se and Te) reveals the presence of two equivalent σ‐holes, one on each chalcogen atom. These CX2 molecules interact with diazine giving rise to supramolecular interactions. Wiberg bond index and second‐order perturbation theory analysis in NBO were performed to better understand the nature of the chalcogen bond interaction.

Single crystal X-ray studies and Hirshfeld surface analysis of ethoxy phenyl substituted chalcone derivatives

Abstract The single crystal X-ray of three chalcone derivatives, (2E)-3-(2-chlorophenyl) -1-(4-ethoxyphenyl) prop-2-en-1-one (I), (2E)-3-(3-chlorophenyl)-1-(4-ethoxyphenyl)prop-2-en-1-one (II) and (2E)-1-(4-ethoxyphenyl)-3-(4-methoxyphenyl)prop-2-en-1-one (III) was determined. The compound (I) crystallized in triclinic P−1 crystal system and in the asymmetric unit of the compound (I), two molecules were present. The conformational differences between molecule A and B indicated with the dihedral angles of 3.47 (2)° (A) and 8.12 (16)° (B), measured between chlorophenyl ring (C1A/B-C6A/B) and methoxy phenyl (C10A/B–C16A/B). Similarly the compound (II) crystallized in monoclinic P−1 crystal system and in the asymmetric unit of the compound (II), two molecules were present. The conformational differences between molecule A and B with the dihedral angles of 4.50 (11)° (A) and 3.94 (11)° (B) was measured between terminal phenyl rings. The compound (III) crystallized in monoclinic, P21/n, with a dihedral angle between two terminal phenyl rings is 13.18 (7)°, indicating the near planarity of the compound. The intramolecular hydrogen bond of the types C—H…O is observed in all compounds (I), (II) and (III). In the crystal structures (I), (II) and (III), C—H…π intermolecular interaction was found in all compounds. The intermolecular hydrogen bond of the type C—H…O was present in compounds (I) and (II). The Hirshfeld surface analysis was carried for compounds (I), (II) and (III). Intercontacts C C, C H, C O, H H and O H were common in all compounds which contributed more to the Hirshfeld surfaces. The electrostatic potential surfaces were drawn to understand electrophilic and nucleophilic regions on the molecule.

Structural, vibrational and quantum chemical investigations for 6,7-dichloro-2-methyl-5,8-quinolinedione. Cytotoxic and molecular docking studies

6,7-Dichloro-2-methyl-5,8-quinolinedione was investigated using different experimental methods as well as a variety of various quantum chemical calculations in order to characterize its molecular structure as a potential anticancer active compound. We used X-ray diffraction, IR spectrum analysis supplemented by the density functional theory (DFT) calculations, molecular electrostatic potential (MEP) and molecular orbital (HOMO, LUMO) analyses. The analyzes were carried out with respect to 6,7-dichloro-5,8-quinolinedione. It was found that introduction of the methyl group at the C-2 position distinctly affected the crystal structure, formation of H-bonds and the carbonyl stretching IR bands of the title compound. The molecular electrostatic potential map showed how the electrophilic and nucleophilic regions are located in the molecule. The intra- and intermolecular bonding and interaction between bonds were interpreted using the Natural Bond Orbital (NBO) and Natural Localized Molecular Orbital (NLMO) analysis.The title compound was tested for its anticancer activity in vitro against the several human cancer cell lines. 6,7-Dichloro-2-methyl-5,8-quinolinedione showed a higher cytotoxic activity against cancer cell lines containing a higher level of NQO1 enzyme, like melanoma (C-32) and breast (MCF-7) cancer cell lines. The molecular docking was used to examine the probable interaction between the molecule of the tested compound and the NQO1 enzyme. The analysis showed that the 5,8-quinolinedione moiety of the title compound formed a hydrophobic interaction with phenylalanine (Phe 178), tyrosine (Tyr 126 and Tyr 128) and FAD cofactor.

Synthesis, spectral characterization and X-ray crystal structure studies of 3-(benzo[d][1,3]dioxol-5-yl)-5-(3-methylthiophen-2-yl)-4,5-dihydro-1H-pyrazole-1-carboxamide: Hirshfeld surface, DFT and thermal analysis

A novel pyrazole derivative, 3-(benzo[d][1,3]dioxol-5-yl)-5-(3-methylthiophen-2-yl)-4,5-dihydro-1H-pyrazole-1-carboxamide was synthesized and characterized by elemental analysis, FT-IR, NMR (1H and 13C), MS, UV–visible spectra and finally the structure was confirmed by the single crystal X-ray diffraction studies. The title compound (C16H15N3O3S) crystallized in the triclinic crystal system, with the space group Pī. A dihedral angle of 65.84(1)° between the pyrazole and the thiophene rings confirms the twisted conformation between them. The X-ray structure revealed that the pyrazole ring adopts an E-form and an envelope conformation on C7 atom. The crystal and molecular structure of the title compound is stabilized by inter molecular hydrogen bonds. The compound possesses three dimensional supramolecular self-assembly, in which CH⋯O and NH⋯O chains build up two dimensional arrays, which are extended to 3D network through CH···Cg and CO···Cg interactions. The structure also exhibits intramolecular hydrogen bonds of the type NH⋯N and π···π stacking interactions, which contributes to the crystal packing. Further, Hirshfeld surface analysis was carried out for the graphical visualization of several short intermolecular interactions on the molecular surface while the 2D finger-print plot provides percentage contribution of each individual atom-to-atom interactions. The thermal decomposition of the compound has been studied by thermogravimetric analysis. The molecular geometries and electronic structures of the compounds were fully optimized, calculated with ab-initio methods by HF, DFT/B3LYP functional in combination of different basis set with different solvent environment and the structural parameters were compared with the experimental data. The Mulliken atomic charges and molecular electrostatic potential on molecular van der Waals (vdW) surface were calculated to know the electrophilic and nucleophilic regions of the molecular surface. Nonlinear optical properties of the title compound were also discussed based on the polarizability and hyperpolarizability values.

Synthesis, spectral and X-ray crystal structure of 3-(3-methoxyphenyl)-5-(3-methylthiophen-2-yl)-4,5-dihydro-1H-pyrazole-1-carboxamide: Hirshfeld surface, DFT calculations and thermo-optical studies

Abstract Novel pyrazole derivative, 3-(3-methoxyphenyl)-5-(3-methylthiophen-2-yl)-4,5-dihydro-1H-pyrazole-1-carboxamide was synthesized, characterized by NMR, mass spectra, FT-IR, UV–Visible, TG-DTG and finally the three dimensional structure was confirmed by single crystal X-ray diffraction studies. A dihedral angle of 78.51(13)° between the pyrazole and the thiophene rings confirms the twisted conformation between the rings. C—H•••O and N—H•••O hydrogen bond interactions are extended through 3D network to form R22(8) supramolecular motif. The compound was found to be thermally stable up to 190 °C. Further, the intermolecular interactions of the crystal structure were analysed by Hirshfeld surface analysis. The molecular geometries and electronic structures of the compound were optimized, calculated with ab-initio methods. The electrophilic and nucleophilic regions of the molecular surface were identified. The solvent effects on the structural parameters were studied using different solvents. Non-linear optical properties of the title compound were investigated.

Synthesis, spectroscopic and DFT studies of novel 4-(morpholinomethyl)-5-oxo-1-phenylpyrrolidine-3-carboxylic acid

A novel 4-(morpholinomethyl)-5-oxo-1-phenylpyrrolidine-3-carboxylic acid has been synthesized and its structural elucidation has been done by UV, FT-IR, 1H and 13C NMR spectroscopy. All quantum chemical calculations were carried out at level of density functional theory (DFT) with B3LYP function using 6-31G (d, p) basis atomic set. AIM approach has been incorporated for the analysis of various intermolecular interactions. Polarizability and hyperpolarizabilities values have been calculated along with the exploration of nonlinear optical properties of the title compound. DFT computed total first static hyperpolarizability (β0 = 0.2747 × 10−30 esu) indicates that title molecule could be an area of interest as an attractive future NLO material. For the analysis of thermal behaviour of title molecule, thermodynamic properties such as heat capacity, entropy and enthalpy change at various temperatures have been calculated. The NBO computations were done for the correlation of possible transitions with the electronic transitions. Electrophilic and nucleophilic regions were identified with the help of MESP plot. Determination of energy gap has been done by using HOMO and LUMO energy values, along with the computation of electronegativity and electrophilicity indices.

Experimental and theoretical studies on photoluminescent Zn(II) host complex with an open book structure: Implication on potential bioactivity and comparison with its ligand and Zn(II), Pd(II) siblings

A novel inclusion Zn(II) complex with water guest molecule is synthesized from 6,6′-diethoxy-2,2′-[2,2-dimethylpropane-1,3-diylbis(nitrilomethylidyne)]-diphenol salen-type Schiff base (H2L) and is characterized through single crystal XRD studies, IR, UV–Vis methods. Thermal profile is studied using TG-DTG–DSC method. Single crystal XRD analysis reveals a rare open book structure for the complex and an interesting star-like supramolecular assembly. The emission properties of the complex is compared with that of the ligand, pseudo-inclusion and inclusion compounds from Zn(II) and Pd(II) ions prepared from the same ligand. Hirshfeld surface for the compounds were mapped with various functions and further quantification of intermolecular interactions was made through the generation of 2D finger print plots. To dissect the nucleophilic and electrophilic regions on the molecular surface, ESP plots of the compounds are generated. Further DFT calculations are done at B3LYP/def2-TZVP level of theory to optimize the geometry of the compounds and to compare frontier orbitals and charge distribution among the compounds. Molecular docking of the compounds with B-DNA dodecamer and Human Serum Albumin (HSA) is performed to gain an insight on the structure–activity relationship of these compounds.

Experimental and theoretical investigations on Pd(II) host-guest compound: Deciphering the structural and electronic features of a potential bioactive complex

A Pd(II) complex from N,N′-bis(2-hydroxy-3-ethoxybenzylidene)butane-1,4-diamine salen-type ligand has been synthesized and characterised using single crystal XRD analysis, elemental analysis, IR and UV–Vis spectroscopic methods. Thermal profile of the compound is investigated using TG-DTG-DSC method. The quantification of intermolecular interactions and surface morphology has been done using Hirshfeld surface study mapped using various functions like dnorm, shape index and curvedness. ESP analysis is done to visualize the electrophilic and nucleophilic regions in the complex. Geometry optimization of the structure is done using DFT at B3LYP/def2-TZVP level of theory. Frontier orbital analysis reveals the kinetical stability and chemical inertness of the complex. A detailed charge distribution analysis is done using different analytical methods like Mulliken, Löwdin, NPA and AIM methods. Further bond order analysis and topological analysis are also done. Finally the bioactivity of the titled complex is checked using molecular docking method on both DNA and protein.

Intermolecular interactions in crystal structure, Hirshfeld surface, characterization, DFT and thermal analysis of 5-((5-bromo-1H-indol-3-yl)methylene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione indole

Condensation reaction of 5-bromo-1H-indole-3-carbaldehyde and 1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione in ethanol under reflux conditions furnished the formation of 5-((5-bromo-1H-indol-3-yl)methylene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione indole in a very good yield. The desired compound is characterized by spectroscopic and thermal tools, additionally the structure was confirmed by X-ray single crystal diffraction. Visually analysis of desired crystal structure using Hirshfeld surface revealed several short intermolecular connections on the molecule surface while the 2D finger-print draw evaluated the atom-to-atom interactions percentages.The structures of the monomer and the dimer of the product that are obtained from the B3LYP/6-31G(d,p) molecular geometry optimizations were compared with the XRD experimental one. Electronic spectra are assigned on the basis of the TD-DFT results and the molecular orbital (MO) energy level diagrams showing the different MOs included in these transitions are explored. The electrophilic and nucleophilic regions are shown using molecular electrostatic potential map. The GIAO method is used to compute and compare the NMR chemical shifts. The desired organic compound revealed a good thermal stability up to 215 °C.

Prospects for 207Pb solid-state NMR studies of lead tetrel bonds.

The feasibility and value of 207Pb solid-state NMR experiments on compounds featuring lead tetrel bonds is explored. Although the definition remains to be formalized, lead tetrel bonds may be qualitatively described as existing when there is evidence of a net attractive interaction between an electrophilic region associated with lead in a molecular entity and a nucleophilic region in another, or the same, molecular entity. Unambiguous identification of lead tetrel bonds can be challenging due to the hypervalent tendency of lead. We report here a series of 207Pb solid-state NMR experiments on five metal-organic frameworks featuring lead coordinated to hydrazone-based ligands. Such frameworks may be held together in part by lead tetrel bonds. The acquisition of 207Pb solid-state NMR spectra for such materials is feasible and is readily accomplished using a combination of magic-angle spinning and Carr-Purcell-Meiboom-Gill methods in moderate to low applied magnetic fields. The lead centres are characterized by 207Pb isotropic chemical shifts ranging from -426 to -2591 ppm and chemical shift tensor spans ranging from 910 to 2681 ppm. Careful inspection of the structures of the compounds and the literature 207Pb NMR data may suggest that a tetrel bond to lead results in chemical shift parameters which are intermediate between those which are characteristic of holodirected and hemidirected lead coordination geometries. Challenges associated with DFT computations of the 207Pb NMR parameters are discussed. In summary, the 207Pb data for the compounds studied herein show a marked response to the presence of non-coordinating electron-rich moieties in close contact with the electrophilic surface of formally hemidirectionally coordinated lead compounds.

Tetrel, pnictogen and chalcogen bonds identified in the gas phase before they had names: a systematic look at non-covalent interactions

The terms tetrel bond, pnictogen bond and chalcogen bond were coined recently to describe non-covalent interactions involving group 14, 15 and 16 atoms, respectively, acting as the electrophilic site that seeks a nucleophilic region of another molecule, for example a non-bonding electron pair or π-electron pair of a Lewis base. Many complexes containing these non-covalent bonds were identified and characterised in isolation in the gas phase by rotational and vibrational spectroscopy long before they were given these names. In this article, the geometries so determined for selected examples of complexes of each type are rationalised in terms of the molecular electrostatic surface potentials of the component molecules. Examples of chalcogen-bonded complexes considered are based mainly on sulfur dioxide, with the region near the sulfur atom as the electrophilic site that interacts with n-electron and π-electron pairs for a range of simple Lewis base molecules. For tetrel bonds, the examples discussed involve the carbon atom of carbon dioxide as the electrophilic centre, while for pnictogen bonds the central nitrogen of the closely related molecule nitrous oxide is chosen. Geometrical similarities within each series allow simple definitions of each type of non-covalent bond that are conformal with that recently advanced for the halogen bond, a related non-covalent interaction.

Molecular and supramolecular properties of nitroaromatic thiosemicarbazones: Synthesis, spectroscopy, X-ray structure elucidation and DFT calculations

The reactions of 6-nitropiperonal with H2NNHC(S)NHR, R = Me, Et, Ph or H, afforded four nitroaromatic thiosemicarbazones 1–4, respectively. 1–4 were characterized by elemental analysis (CHN), FTIR, and 1H and 13C{1H} NMR spectroscopy. In addition, the crystal structures of 2 and 3 were determined by single-crystal X-ray diffraction. Our X-ray structural results have shown that the nitropiperonal and thiosemicarbazone moieties exhibit an almost coplanar arrangement for both 2 and 3. Moreover, they establish 2-D networks along the [111] base vector by means of classical and nonclassical hydrogen bonds. Electronic and spectroscopic properties of 1–4 were investigated at the DFT B3LYP/6-311G** level of calculation. The CS group of 1–4 constitutes a nucleophilic region, whereas the NO2 group defines an electrophilic centre, as expected. Furthermore, a DFT vibrational analysis of 4 allowed a reliable assignment of the thiosemicarbazone-based vibrations. Also, a good agreement between theoretical and experimental 13C chemical shift values was obtained for 1–4.

Spectroscopic characterization of 1-[3-(1H-imidazol-1-yl)propyl]-3-phenylthiourea and assessment of reactive and optoelectronic properties employing DFT calculations and molecular dynamics simulations

IR and Raman spectra of 1-[3-(1H-imidazol-1-yl)propyl]-3-phenylthiourea (HIPPT) have been recorded in the solid phase and the vibrational wave numbers are calculated theoretically by B3LYP/6-31G(d,p) (6D, 7F) method. All the fundamental vibrational modes have been assigned using potential energy distribution values and the molecular structure was analyzed in terms of parameters like bond length, bond angles and dihedral angles. The ring breathing mode of the phenyl ring is observed at 1016 cm−1 in the IR spectrum, 1014 cm−1 in the Raman spectrum and at 1014 cm−1 theoretically. The values of polarizability and hyperpolarizabilities were calculated and nonlinear optical properties are discussed. The HOMO-LUMO plot reveals the charge transfer possibilities in the molecule. The NBO analysis was computed and possible transitions were correlated with the electronic transitions. In the title compound, the imidazole ring and CH2 groups are tilted from each other and the thiourea group is tilted from the phenyl ring. Using MEP plot the electrophilic and nucleophilic regions are identified. Local reactivity properties were investigated by analysis of ALIE surfaces and Fukui functions. Oxidation and degradation properties were initially assessed by calculation of bond dissociation energies of all single acyclic bonds. Determination of atoms with pronounced interactions with water molecules was performed by calculation of radial distribution functions after molecular dynamics simulations. Chargehopping rates were calculated within Marcus semi-empiric approach, employing both DFT calculations and MD simulations. The molecular docking computational predictions were complemented by the in vitro antibacterial activity evaluation.

Study the effect of F17S mutation on the chimeric Bacillus thermocatenulatus lipase.

Lipases (triacylglycerol acylhydrolase, EC 3.1.1.3) are one of the highest value commercial enzymes as they have potential applications in biotechnology for detergents, food, pharmaceuticals, leather, textiles, cosmetics, and paper industries; and are currently receiving considerable attention because of their potential applications in biotechnology. Bacillus thermocatenulatus Lipase 2 (BTL2) is one of the most important research targets, because of its potential industrial applications. In this study, the effect of substitution Phe17 with Ser in mutated BTL2 lipase, which conserved pentapeptide (112Ala-His-Ser-Gln-Gly116) was replaced with similar sequences (207Gly-Glu-Ser-Ala-Gly211) of Candida rugosa lipase (CLR) at the nucleophilic elbow region. Docking results confirmed the mutated lipase to be better than the chimeric lipase. So, cloning was conducted, and the mutated and chimeric btl2 genes were expressed in Escherichia coli, and then the enzymes were purified by anion exchange chromatography. The mutation increased lipase lipolytic activity against most of the applied substrates, with the exception of tributyrin when compared with chimeric lipase. Further, the mutated lipase exhibited higher activity than the chimeric lipase at all temperatures. Optimum pH of the mutated lipase was obtained at pH 9.5, which was more than the chimeric one. Enzyme activity of the mutated lipase in the presence of organic solvents, detergents, and metal ions was also improved than the chimeric lipase.

Analysis Spectroscopy of the Absorption of Calcium Carbonate on Graphene/Polyurethane Composites Applied Computational Simulation and Artificial Neuronal Networks

One of the most important applications of graphene is in the field of polymer nanocomposites, where graphene is introduced as filler with the aim to improve their chemical and physical properties. Such as polystyrene (PS), PMMA, PVA, polypropylene (PP), epoxy, polyester, silicon foams, polyurethanes (PU) and polycarbonates (PC), graphene-based nanomaterials have been utilized in a myriad of bioapplications (e.g., drugs and gene delivery, nanomedicine, bioimaging and potential cancer therapies). The graphene, Polyurethane (PU), calcium carbonate (CC) and absorption of CC in graphene/PU composite, respectively were studied using theoretical calculations like Gibbs free energy, log P, Fourier Transform Infrared (FTIR) and electrostatic potential. FTIR spectroscopy reveals information about the molecular interactions of chemical components and is useful for characterization of composite. Nucleophilic and electrophilic regions were calculated using the electrostatic potential. It was determined that the hydrophilic (log P, octanol–water distribution constant) values play an important role in the absorption process of CC.

Indole-containing new types of dyes and their UV–vis and NMR spectra and electronic structures: Experimental and theoretical study

Indole containing dyes were synthesized via a simple method with high yield. These molecules have different colors and UV–vis spectra of them were recorded. Impact of solvents on absorbances was investigated and it was observed that basic solvent such as DMF and pyridine have blue shift. TD-DFT calculations were done and results were compared with experimental data. NMR data of molecules were analyzed and tautomeric forms of colorants and their ratio were determined. It was find out that two tautomers might be formed in solution, called indole and indolenine form. HOMO-LUMO and energy gaps were calculated and plotted. Furthermore, molecular electrostatic potentials were simulated to find out electrophilic and nucleophilic regions.

Computational studies of stable hexanuclear CulAgmAun(l + m + n = 6;l,m,n > 0) clusters

A DFT study was carried out on the ground state structures of ternary CulAgmAun (l + m + n = 6) clusters, with the aim of investigating changes of thermal and kinetic stabilities as an effect of composition, as well as the composition dependence of the electrostatic potential, of stable planar structures. DFT optimizations were performed using the PBE functional and the SDD basis set. All the optimized structures adopt planar geometries with bent triangular structures. Calculated binding energy values are in the range 1.5–1.9 eV/atom, which shows their thermal stability. The predicted HOMO-LUMO energy gap values are in the semiconductor region, providing a qualitative indication of a moderate kinetic stability. NBO analyses indicate the existence of two mechanisms promoting planar structural stability, one due to bonding-antibonding orbital interaction, and the other one due to the well-known spd hybridization. Wiberg indices were obtained showing interatomic bonding. Electrostatic potential calculations show the existence of nucleophilic attack regions preferentially around silver and copper atoms located at the vertices while electrophilic attack regions are found in the vicinity of gold atoms over the cluster plane. Apparently, charge transfer occurs toward gold from silver and copper atoms when the concentration is favorable in the proximity of gold atoms. In particular, if the small ternary clusters discussed here contain only one gold atom, then a high electron density is observed at the site of this gold atom. © 2016 Wiley Periodicals, Inc.

The Halogen Bond.

The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

A halogen bond does not dictate the conformational preferences of cis-1,3-disubstituted cyclohexanes.

Halogen bonds are defined as interactions between halogens and a Lewis base in which the halogen (X) acts as the electrophilic species, and is typically explained by the presence of a σ-hole at the end of the C-X bond. Despite the important role of the halogen bond in intermolecularly interacting species, e.g. in acid-base reactions, enzyme inhibition and the supramolecular architecture, this interaction was not found to control the conformational equilibrium of some small model molecules, namely cis-1,3-disubstituted cyclohexanes. In addition, the attraction between the electrophilic (σ-hole) and nucleophilic regions is used to explain that the halogen bond was weaker than that in the species with parallel C-X bonds. Therefore, intramolecular halogen bonds should be used with caution to explain the conformational stability of organic compounds.

Conformational stability, molecular structure, vibrational, electronic, 1H and 13C spectral analysis of 3-pyridinemethanol using ab-initio/DFT method

The FT-IR and FT-Raman spectra of 3-pyridinemethanol (3PYRM) have been recorded in the regions 4000–400 and 4000–100 cm−1 respectively. The vibrational analysis of 3PYRM was carried out using wavenumbers computed by HF and DFT (B3LYP) methods with 6-311++G (d, p) basis set, along with experimental values. The conformational analyses were performed and the energies of the different possible conformers were determined. The total electron density and MESP surfaces of the molecules were constructed using B3LYP/6-311++G (d, p) method to display nucleophilic and electrophilic region globally. The HOMO and LUMO energies were measured and different reactivity descriptors are discussed the active sites of the molecule. Natural Bond Orbital Analysis is discussed and possible transition are correlated with the electronic transitions. Milliken's net charges and the atomic natural charges are also predicted. The 13C and 1H NMR chemical shifts were computed at the B3LYP/6-311++G (2d, p) level by applying GIAO theory and compared with the experimental spectra recorded using the high resolution of 100 MHz and 400 MHz NMR spectrometer with electromagnetic field strength 9.1T, respectively. The temperature dependence of the thermodynamic properties; heat capacity, entropy and enthalpy for the title compounds were also determined by B3LYP/6-311++G (d, p) method.