Ivelina Georgieva

DFT-based molecular modeling and vibrational study of the La(III) complex of 3,3′-(benzylidene)bis(4-hydroxycoumarin)

AbstractMolecular modeling of the La(III) complex of 3,3′-(benzylidene)bis(4-hydroxycoumarin) (PhDC) was performed using density functional theory (DFT) methods at B3LYP/6-31G(d) and BP86/TZP levels. Both Stuttgart-Dresden effective core potential and ZORA approximation were applied to the La(III) center. The electron density distribution and the nucleophilic centers of the deprotonated ligand PhDC2- in a solvent environment were estimated on the basis of Hirshfeld atomic charges, electrostatic potential values at the nuclei, and Nalewajski-Mrozek bond orders. In accordance with the empirical formula La(PhDC)(OH)(H2O), a chain structure of the complex was simulated by means of two types of molecular fragment: (1) two La(III) cations bound to one PhDC2- ligand, and (2) two PhDC2- ligands bound to one La(III) cation. Different orientations of PhDC2-, OH- and H2O ligands in the La(III) complexes were investigated using 20 possible [La(PhDC2-)2(OH)(H2O)]2- fragments. Energy calculations predicted that the prism-like structure based on “tail-head” cis-LML2 type binding and stabilized via HO...HOH intramolecular hydrogen bonds is the most probable structure for the La(III) complex. The calculated vibrational spectrum of the lowest energy La(III) model fragment is in very good agreement with the experimental IR spectrum of the complex, supporting the suggested ligand binding mode to La(III) in a chain structure, namely, every PhDC2- interacts with two La(III) cations through both carbonylic and both hydroxylic oxygens, and every La(III) cation binds four oxygen atoms of two different PhDC2-. FigureLow energy prism-like model fragment, [La(PhDC2-)2(OH)(H2O)]2-, optimized at BP86/TZP level of theory

Intramolecular Charge-Transfer Excited-State Processes in 4-(N,N-Dimethylamino)benzonitrile: The Role of Twisting and the πσ* State.

The structural processes leading to dual fluorescence of 4-(dimethylamino)benzonitrile in the gas phase and in acetonitrile solvent were investigated using a combination of multireference configuration interaction (MRCI) and the second-order algebraic diagrammatic construction (ADC(2)) methods. Solvent effects were included on the basis of the conductor-like screening model. The MRCI method was used for computing the nonadiabatic interaction between the two lowest excited ππ* states (S2(La, CT) and S1(Lb, LE)) and the corresponding minimum on the crossing seam (MXS) whereas the ADC(2) calculations were dedicated to assessing the role of the πσ* state. The MXS structure was found to have a twisting angle of ∼50°. The branching space does not contain the twisting motion of the dimethylamino group and thus is not directly involved in the deactivation process from S2 to S1. Polar solvent effects are not found to have a significant influence on this situation. Applying Cs symmetry restrictions, the ADC(2) calculations show that CCN bending leads to a strong stabilization and to significant charge transfer (CT). Nevertheless, this structure is not a minimum but converts to the local excitation (LE) structure on releasing the symmetry constraint. These findings suggest that the main role in the dynamics is played by the nonadiabatic interaction of the LE and CT states and that the main source for the dual fluorescence is the twisted internal charge-transfer state in addition to the LE state.

Molecular structure and spectroscopic studies on novel complexes of coumarin-3-carboxylic acid with Ni(II), Co(II), Zn(II) and Mn(II) ions based on density functional theory.

Novel Ni(II), Co(II), Zn(II) and Mn(II) complexes of coumarin-3-carboxylic acid (HCCA) were studied at experimental and theoretical levels. The complexes were characterised by elemental analyses, FT-IR, (1)H NMR, (13)C NMR and UV-Vis spectroscopy and by magnetic susceptibility measurements. The binding modes of the ligand and the spin states of the metal complexes were established by means of molecular modelling of the complexes studied and calculation of their IR, NMR and absorption spectra at DFT(TDDFT)/B3LYP level. The experimental and calculated data verified high spin Ni(II), Co(II) and Mn(II) complexes and a bidentate binding through the carboxylic oxygen atoms (CCA2). The model calculations predicted pseudo octahedral trans-[M(CCA2)(2)(H(2)O)(2)] structures for the Zn(II), Ni(II) and Co(II) complexes and a binuclear [Mn(2)(CCA2)(4)(H(2)O)(2)] structure. Experimental and calculated (1)H, (13)C NMR, IR and UV-Vis data were used to distinguish the two possible bidentate binding modes (CCA1 and CCA2) as well as mononuclear and binuclear structures of the metal complexes.

Solvatochromic and ionochromic effects of Iron(II)bis(1,10-phenanthroline)dicyano: a theoretical study.

Solvatochromic and ionochromic effects of the iron(II)bis(1,10-phenanthroline)dicyano (Fe(phen)(2)(CN)(2)) complex were investigated by means of combined DFT/TDDFT calculations using the PBE and B3LYP functionals. Extended solvation models of Fe(phen)(2)(CN)(2) in acetonitrile and aqueous solution, as well as including interaction with Mg(2+), were constructed. The calculated vertical excitation energies reproduce well the observed solvatochromism in acetonitrile and aqueous solutions, the ionochromism in acetonitrile in the presence of Mg(2+), and the absence of ionochromic effect in aqueous solution. The vertical excitation energies and the nature of the transitions were reliably predicted after inclusion of geometry relaxation upon aqueous micro- and global solvation and solvent polarization effect in the TDDFT calculations. The two intense UV-vis absorption bands occurring for all systems studied are interpreted as transitions from a hybrid Fe(II)(d)/cyano N(p) orbital to a phenanthroline pi* orbital rather than a pure metal-to-ligand-charge transfer (MLCT). The solvatochromic and ionochromic blue band shifts of Fe(phen)(2)(CN)(2) were explained with preferential stabilization of the highest occupied Fe(II)(d)/cyano N(p) orbitals as a result of specific interactions with water solvent molecules or Mg(2+) ions in solution. Such interactions occur through the CN(-) groups in the complex, and they have a decisive role for the observed blue shifts of UV-vis absorption bands.

Lanthanide and transition metal complexes of bioactive coumarins: Molecular modeling and spectroscopic studies

The present paper summarizes theoretical and spectroscopic investigations on a series of active coumarins and their lanthanide and transition metal complexes with application in medicine and pharmacy. Molecular modeling as well as IR, Raman, NMR and electronic spectral simulations at different levels of theory were performed to obtain important molecular descriptors: total energy, formation energy, binding energy, stability, conformations, structural parameters, electron density distribution, molecular electrostatic potential, Fukui functions, atomic charges, and reactive indexes. The computations are performed both in gas phase and in solution with consideration of the solvent effect on the molecular structural and energetic parameters. The investigations have shown that the advanced computational methods are reliable for prediction of the metal-coumarin binding mode, electron density distribution, thermodynamic properties as well as the strength and nature of the metal-coumarin interaction (not experimentally accessible) and correctly interpret the experimental spectroscopic data. Known results from biological tests for cytotoxic, antimicrobial, anti-fungal, spasmolytic and anti-HIV activities on the studied metal complexes are reported and discussed.

Adsorption of the Herbicide 4-Chloro-2-methylphenoxyacetic Acid (MCPA) by Goethite

Interaction between the goethite surface and 4-chloro-2-methylphenoxyacetic acid (MCPA) herbicide was studied using density functional theory (DFT) calculations combined with molecular dynamics (MD). The important step made here lies in the use of a periodic DFT method enabling the study of a mineral surface of different protonation states, in strong contrast with previous molecular modeling studies limited to single protonation state corresponding to the point of zero charge. Different surface OH groups and MCPA proton states were used to mimic the strong effects of pH on the outer- and inner-sphere surface complexes that are theoretically possible, together with their binding energies, and their bond lengths. Modeling both a solvated and a protonated (110) goethite surface provided a major breakthrough in the acidic adsorption regime. An outer-sphere complex and a monodentate inner-sphere complex with the neutral MCPA molecule were found to be the most energetically stable adsorbate forms. MD modeling predicted that the latter forms via the sharing of the carbonyl oxygen between the MCPA carboxylate group and a singly coordinated surface hydroxyl group, releasing an H2O molecule. All the other complexes, including the bidentate inner-sphere complex, had higher relative energies and were therefore less likely. The two most likely DFT-optimized structures were used to constrain a surface complexation model applying the charge distribution multisite complexation (CD-MUSIC) approach. The adsorption constants for the complexes were successfully fitted to experimental batch equilibrium data.

DFT study of hydrogen-bonded dimers and tetramer of glyoxilic acid oxime

Abstract DFT study of hydrogen-bonded dimers and tetramer of glyoxilic acid oxime (GAO) has been performed at B3LYP/6-31G* and B3LYP/6-31++G** levels of the theory. The N⋯HO and O⋯HO hydrogen bondings in the self-assembling structures studied have been estimated from intermolecular distances, enthalpy of stabilization, hydrogen-bonding energies and AIM electron density at the hydrogen bond critical points. The calculated hydrogen-bonding energies of various GAO dimers suggested a cooperative interaction in the cyclic dimers and tetramer. The comparative study of chain aggregate with both head-to-head and tail-to-tail bondings and chain aggregate only with head-to-tail bondings, showed that the latter is enthalpically preferred in agreement with the crystal structure of GAO. Harmonic frequencies for the monomer, five dimers and tetramer have been calculated and discussed as to the changes in the most sensitive to the complexation vibrations and as to the strengths of the O⋯HO and N⋯HO hydrogen bondings. Vibrational analysis at B3LYP/6-31G* level confirmed the suggestion for a cooperativity in the cyclic H-bonded complexes. Natural population analysis was performed to predict electrostatic interactions in the cyclic H-bonded complexes. The π-delocalization was estimated on the basis of the calculated AIM ellipticity.

IR and Raman study of Pt(II) and Pd(II) complexes of amino substituted phosphine oxides: Normal coordinate analysis

Abstract IR and Raman spectra of Pt(dapo) 2 Cl 2 and Pd(dapo) 2 Cl 2 (dapo=dimethyl(aminomethyl)phosphine oxide) have been measured in the 200–4000 cm −1 frequency range. Both the IR and Raman spectra show that dimethyl(aminomethyl)phosphine oxide ligands are monodentate coordinate. The results from the normal coordinate analysis calculations confirm the monodentate coordination of the ligands in agreement with some literature data. For Pd(dapo) 2 Cl 2 complex the possibility for bidentate coordination of one dapo ligand is also considered.

Spectroscopic studies, DFT calculations, and cytotoxic activity of novel silver(I) complexes of hydroxy ortho-substituted-nitro-2H-chromen-2-one ligands and a phenanthroline adduct.

Silver(I) complexes of coumarin-based ligands and one of their phenanthroline (phen) adducts have been prepared and characterized using microanalytical data, molar conductivity, IR, (1)H and (13)C NMR, UV-Vis, and atomic absorption (AAS) spectroscopies. The binding modes of the coumarin-based ligands and the most probable structure of their Ag(I) complexes were predicted by means of molecular modeling and calculations of their IR, NMR, and absorption spectra using density functional theory (DFT). The cytotoxicity of the compounds studied against human-derived hepatic carcinoma cells (Hep-G2) and a renal cancer cell line (A498) showed that the complexes were more cytotoxic than the clinically used chemotherapeutic, mitoxantrone. The compounds showed little interaction with DNA and also did not show nuclease activity but manifested excellent superoxide dismutase activity which may indicate that their mechanism of action is quite different to many metal-based therapeutics.

Multiple adsorption of NO on cobalt-exchanged chabazite, mordenite, and ferrierite zeolites: A periodic density functional theory study

The adsorption of NO on Co(II)-exchanged chabazite (CHA), mordenite (MOR), and ferrierite (FER) has been investigated by periodic density functional theory calculations. The most stable configurations of Co(II) in alpha and beta sites of the zeolites with two framework Al/Si substitutions at short distances and Al-(Si)(n>1)-Al ordering are used for calculating the adsorption energy of NO molecules on Co(II) cations and at Al framework sites. The less stable configurations of alpha-Co(II)-MOR/FER show larger adsorption energies for one and two NO molecules. The bonding of one, two (and three) NO molecules to alpha/beta-Co(II) sites in CHA/MOR/FER induces a shortening of the N-O bond lengths because electron density is withdrawn from the antibonding orbital of the adsorbed NO molecule. The calculated nu(NO) stretching frequencies of mono- and dinitrosyl complexes at alpha/beta-Co(II)-MOR/FER are in good agreement with the experimental data. NO molecules adsorbed on alpha-Co(II)-MOR and on alpha-Co(II)-FER show similar NO stretching frequencies as nitrosyl complexes in Co(II)-MOR/-FER/-ZSM-5. Mononitrosyl complexes of alpha/beta-Co(II)-MOR/FER display nu(NO) frequencies blueshifted relative to the free NO, while in dinitrosyl complexes both the symmetric and asymmetric components are redshifted compared to the mononitrosyl frequency. The analysis of the vibrational spectra suggests that mononitrosyls are formed by adsorption at cation in both alpha and beta sites in MOR, FER, and ZSM-5, while dinitrosyl complexes exist only at alpha-type Lewis sites. This is important for the understanding of the reduction mechanism of NO to N(2). A larger adsorption capacity of alpha-Co(II)-FER compared to alpha-Co(II)-MOR is predicted.