Density functional theory (DFT) and ab initio investigations of the electronic and molecular structures of the monomer and the dimer of trimethylaluminium

The electronic and molecular structures of the monomer and dimer of trimethylalu-minium have been studied using density functional theory and ab initio MP2 method. The optimized geometry of the monomer Al(CH3)3 is of C3h symmetry, whereas that of the dimer [A1(CH3)3]2 contains a carbon-bridged four-membered ring structure with C2h symmetry. The hydrogen-bridged six-membered ring structure is found to be unstable. The calculated dimerization energy for the four-membered ring structure is 78 kJ/mol, in close proximity to the experimental value of 85.27 kJ/mol.     

Pyridoxylidene aminoguanidine and its copper(II) complexes – Syntheses,structure, and DFT calculations

Two nitrate salts of the well-known, and due to its significant biological activity very important, compound pyridoxylidene aminoguanidine (PLAG) were obtained in the form of single crystals. Thus this ligand is structurally characterized for the first time. In addition, the first data on the structure of a Schiff base of aminoguanidine with the active form of vitamin B₆, i.e. pyridoxal-phosphate, of the formula PLPAG·HCl·2H₂O, are presented. Two new square-pyramidal Cu(II) complexes of PLAG were synthesized and their physicochemical and structural properties analyzed. In these complexes, PLAG is coordinated as a zwitter-ion, in a tridentate ONN manner, via the oxygen atom of the deprotonated phenolic OH-group and nitrogen atoms of the azomethine and imino group of the aminoguanidine moiety. For the first time it was possible to make a comparative analysis of the structural properties of ligand salts and the coordinated ligand, so the effects of coordination could be unequivocally pointed out. Common fragments encountered in ligand structures were compared by half-normal probability plots. Density functional theory calculations have been conducted in order to gain insight into reactive properties of the investigated molecules. Molecular electrostatic potential, average local ionization energy surfaces, and Fukui functions have been calculated in order to obtain further information on the reactive properties.     

Synthesis, molecular structure, spectral properties and antifungal activity of polymethylene-α,ω-bis(N,N- dimethyl-N-dodecyloammonium bromides)

Hexamethylene-1,6-bis-(N,N-dimethyl-N-dodecylammonium bromide), pentamethylene-1,5-bis(N,N-dimethyl-N-dodecylammonium bromide), tetramethylene-1,4-bis(N,N-dimethyl-N-dodecylammonium bromide), trimethylene-1,3-bis(N,N-dimethyl-N-dodecylammonium bromide) and ethylene-1,2-bis(N,N-dimethyl-N-dodecylammonium bromide) have been obtained and characterized by FTIR and NMR spectroscopy. DFT calculations have also been carried out. The optimized bond lengths, bond angles and torsion angles calculated by Hartree-Fock/3-21G(d,p) approach have been presented. MIC values for A. niger, P. chrysogenum, C. albicans have been determined and the relationship between MIC and spacer length has been discussed.     

Vanadiumoxo–aroylhydrazone complexes: Synthesis,structure and DFT calculations

The aroylhydrazone Schiff base ligands (E)-N’-(2-hydroxybenzylidene)benzohydrazide = H₂L¹, (E)-N’-(2-hydroxy-3-methoxybenzylidene)benzohydrazide = H₂L² and = (E)-N’-(5-bromo-2-hydroxybenzylidene)benzohydrazide = H₂L³ gave the vanadium(V)oxo-aroylhydrazone complexes [V^VOL¹(OCH₃)(OHCH₃] (1), [V^VOL²(OCH₃)(OHCH₃]·CH₃OH (2) and [V^VOL³(OCH₃)(OHCH₃] (3) on reaction with vanadium(IV) oxide acetylacetonate. The complexes were characterized by spectroscopic methods in the solid state (IR) and in solution (UV–Vis, ¹H NMR). Single crystal X-ray analysis was performed with 3. In methanol solution six-coordinated V^VOL³(OCH₃)(OHCH₃) was formed. V^IV was oxidized to V^v by aerial oxygen in the synthesis. In the VO₅N coordination sphere the alcohol oxygen lies trans to the oxo oxygen. The general V–O bond length order is oxo < methoxylato < phenoxidic < enolato < alcoholic. The complexes are mononuclear, but intermolecular O–H?N hydrogen bonding affords a zigzag chain. DFT calculations on complex 3 reproduced the geometric parameters, IR and UV–Vis spectroscopic data well in a reasonable range.     

Tacticity of poly(butyl-α-cyanoacrylate) chains in nanoparticles: NMR spectroscopy and DFT calculations

NMR spectroscopy and quantum chemical calculations were applied for structural characterization and determination of the preferred stereochemical sequence distribution of the monomer units in the homopolymer chains of poly(butyl-α-cyanoacrylate) nanoparticles. The stereochemical sequence distribution of the monomer units was defined by analysis of their high-resolution 1D ¹H and ¹³C NMR and 2D J-resolved, ¹H/¹³C HSQC and ¹H/¹³C HMBC NMR spectra. The results were verified by employment of B3LYP/6-31G(d) calculations and are consistent with the preferred tendency of polymer chains of PBCN to adopt syndiotactic placements. The proton and carbon chemical shielding were calculated at BPW91/6-31+G(2d,p) level using the GIAO approach and B3LYP/6-31G(d) optimized geometry.     

Relativistic DFT calculations of the NMR properties and reactivity of transition metal methane σ-complexes: insights on C-H bond activation

Relativistic ZORA DFT methods have been employed to predict the NMR properties of methane and methyl hydride complexes of rhodium and iridium. Two of these compounds, the rhodium methane and the iridium methyl hydride complexes, have been recently characterized by NMR spectroscopy. Calculations reveal that relativistic effects are largely responsible of the high shielding observed for the proton and carbon resonances of the methane moiety. The key steps for the reaction mechanism of C-H cleavage catalyzed by both compounds have been investigated at the relativistic level. Although the structure of the intermediates and TSs for the Rh and Ir complexes is rather similar, subtle differences in the energetics are responsible of the different catalytic activity of the two complexes.     

Crystal and molecular structure of N-(4-nitrophenyl)-β-alanine--its vibrational spectra and theoretical calculations

The N-(4-nitrophenyl)-β-alanine in crystalline form directly by the addition of 4-nitroaniline to the acrylic acid in aqueous solution has been obtained. The title β-alanine derivative crystallizes in the P2(1)/c space group of monoclinic system with four molecules per unit cell. The X-ray geometry of β-alanine derivative molecule has been compared with those obtained by molecular orbital calculations corresponding to the gas phase. In the crystal the molecules related by an inversion center interact via symmetrically equivalent O-H···O hydrogen bonds with O···O distance of 2.656(2) ? forming a dimeric structure. The dimers of β-alanine derivative weakly interact via N-H···O hydrogen bonds between the H atom of β-amine groups and one of O atom of nitro groups. The room temperature powder vibrational (infrared and Raman) measurements are in accordance with the X-ray analysis. In aqueous solution of 4-nitroaniline and acrylic acid, the double CC bond of vinyl group of acrylic acid breaks as result of 4-nitroaniline addition.     

Molecular structure of N,N′-o-phenylene-bis(salicylideneaminato)copper(II) studied by gas-phase electron diffraction and quantum-chemical calculations

The molecular structure of N,N′-o-phenylene-bis(salicylideneaminato)copper(II) (Cu(saloph)) was determined using the combination of gas-phase electron diffraction (GED), mass spectrometry, and quantum-chemical calculations. According to both experimental and theoretical approaches the molecule of Cu(saloph) is planar and possesses C _2v symmetry. Main structural parameters determined by GED experiment are the following (total error is given in a brackets): r _h1(Cu–N) = 1.960(20) Å, r _h1(Cu–O) = 1.913(17) Å, ∠NCuN = 82.7(18)°, ∠OCuO = 91.6(21)°, ∠NCuO = 92.9(9)°. The experimental structural parameters of Cu(saloph) molecules determined by X-ray single crystal analysis and GED experiments were discussed and compared to the theoretical ones.

     

Substituent and solvent effects on electronic structure and spectral property of ReCl(CO)3(N∧N) (N∧N = glyoxime): DFT and TDDFT theoretical studies

The ground- and excited-state structures of five Re(I) halide glyoxime complexes ReCl(CO)(3)(N(∧)N) (N(∧)N = glyoxime (DHG 1), dimethylglyoxime (DMG 2), cyclohexane dione glyoxime (CHDG 3), dibromoglyoxime (DBG 4), and dimethylformylgloxime (DMFG 5)) have been studied with density functional theory (DFT) and configuration interaction with single excitations (CIS) methods. Time-dependent density functional theory/polarized continuum model (TDDFT/PCM) was carried out to predict the absorption and emission spectra in different media. The effect of substituent and solvent has been researched. It is found that electron-donating groups increase the lowest unoccupied molecular orbital (LUMO) energy resulting in the increased highest occupied molecular orbital (HOMO)-LUMO energy gap. The change leads to their absorption spectra blue shifts in the order 1 > 2 > 3, which arises from the HOMO-1 → LUMO. Just the opposite, electron-withdrawing groups lead to the spectra red shifts (5 > 4 > 1) because of the decreased HOMO-LUMO energy gap. The reorganization energy (λ) calculations show that the relatively balanceable charges transfer abilities of 2 will result in the higher efficiency of organic light emitting devices (OLEDs). In addition, both the absorption and the emission spectra display red shifts in different extents with the decrease of solvent polarity.     

DFT Investigation on Spectroscopic Characteristics and Photolysis Mechanisms of α-Phenoxylacetophenone

The photoinduced bond cleavage and quenching of the α-phenoxylacetophenone excitation states can serve as a template to investigate fundamental photochemical processes. In this work, the absorption and emission spectra as well as the photodecomposition mechanisms of α-phenoxylacetophenone were studied. The density functional theory(DFT) calculations revealed that: 1) the absorption spectra in methanol obtained by the M06-2X functional agree well with those by the B3LYP one; 2) the wavelength of the strongest peak acquired with the B3LYP method is slightly higher than the M06-2X one by 20.07 nm; 3) the βC–C bond in S_1 can be broken directly.     

Does the choice of the crystal structure influence the results of the periodic DFT calculations? A case of glycine alpha polymorph GIPAW NMR parameters computations

Glycine is a common amino acid with relatively complex chemistry in solid state. Although several polymorphs (α, β, δ, γ, ε) of crystalline glycine are known, for NMR spectroscopy the most important is a polymorph, which is used as a standard for calibration of spectrometer performance and therefore it is intensively studied by both experimental methods and theoretical computation. The great scientific interest in a glycine results in a large number of crystallographic information files (CIFs) deposited in Cambridge Structural Database (CSD). The aim of this study was to evaluate the influence of the chosen crystal structure of α glycine obtained in different crystallographic experimental conditions (temperature, pressure and source of radiation of α glycine) on the results of periodic DFT calculation. For this purpose the total of 136 GIPAW calculations of α glycine NMR parameters were performed, preceded by the four approaches (“SP”, “only H”, “full”, “full+cell”) of structure preparation. The analysis of the results of those computations performed on the representative group of 34 structures obtained at various experimental conditions revealed that though the structures were generally characterized by good accuracy (R < 0.05 for most of them) the results of the periodic DFT calculations performed using the unoptimized structures differed significantly. The values of the standard deviations of the studied NMR parameters were in most cases decreasing with the number of optimized parameters. The most accurate results (of the calculations) were in most cases obtained using the structures with solely hydrogen atoms positions optimized. © 2018 Wiley Periodicals, Inc.     

DFT study on activation of carbon dioxide by (tBuArN)3M≡N (M=Nb,V,Ta): the electronic structure and activity

The reaction mechanism for the reduction of CO(2) gas activated by (tBuArN)(3)M≡N was studied by the means of density functional theory (DFT) calculations. The calculations indicated that this reaction has a two step reaction mechanism. From our calculations, we found that (tBuArN)(3)Ta≡N held the best activity among the three (tBuArN)(3)M≡N complexes studied. Our results also indicated that the reaction of (tBuArN)(3)M≡N with CO(2) occurred under orbital control involving the HOMO-3 orbital of (tBuArN)(3)M≡N, which could give higher overlapping with the LUMO of the CO(2) molecule. The substitutions on the amino donor ligands studied here took larger effect on the HOMO structure of the (tBuArN)(3)M≡N molecules. The electronic structure of the (tBuArN)(3)M≡N complexes also showed their ability for activating CO(2) molecules, in the order of M = V < Nb < Ta.     

NMR and molecular modelling studies on the interaction of fluconazole with β-cyclodextrin

Background  

Fluconazole (FLZ) is a synthetic, bistriazole antifungal agent, effective in treating superficial and systemic infections caused by Candida species. Major challenges in formulating this drug for clinical applications include solubility enhancement and improving stability in biological systems. Cyclodextrins (CDs) are chiral, truncated cone shaped macrocyles, and can easily encapsulate fluconazole inside their hydrophobic cavity. NMR spectroscopy has been recognized as an important tool for the interaction study of cyclodextrin and pharmaceutical compounds in solution state.     

How delocalized is N,N,N',N'-tetraphenylphenylenediamine radical cation? An experimental and theoretical study on the electronic and molecular structure

The electronic and molecular structure of N,N,N',N'-tetraphenylphenylenediamine radical cation 1(+) is in focus of this study. Resonance Raman experiments showed that at least eight vibrational modes are strongly coupled to the optical charge resonance band which is seen in the NIR. With the help of a DFT-based vibrational analysis, these eight modes were assigned to symmetric vibrations. The contribution of these symmetric modes to the total vibrational reorganization energy is dominant. These findings are in agreement with the conclusions from a simple two-state two-mode Marcus-Hush analysis which yields a tiny electron-transfer barrier. The excellent agreement of the X-ray crystal structure analysis and the DFT computed molecular structure of 1(+) on one hand as well as the solvent and solid-state IR spectra and the DFT-calculated IR active vibrations on the other hand prove 1(+) adopts a symmetrical delocalized Robin-Day class III structure both in the solid state and in solution.     

Molecular and supramolecular properties of a Hg(II) complex with (E)-N,N′-bis(2-pyridyl)iminoisoindoline: synthesis,spectroscopy, X-ray structure and Hirshfeld surface analyses,and DFT calculations

A scarcity of metal complexes containing (E)-N,N′-bis(heteroaryl)iminoisoindolines has prompted us to investigate the coordinating ability and supramolecular behavior of (E)-N,N′-bis(2-pyridyl)iminoisoindoline (2-pyimiso), a versatile iminobis(pyridyl) ligand. The 1:1 reaction of HgCl₂ with 2-pyimiso in MeOH afforded a dinuclear complex, [{HgCl(2-pyimiso)}₂(μ-Cl)₂] (1). The complex has been characterized by elemental microanalysis, vibrational spectroscopy (FTIR and FT-Raman) and ¹H NMR spectroscopy. DFT calculations at the B3LYP-D3/LACV3P** level have been used in support of our vibrational analysis. Single-crystal X-ray diffraction data have shown that the coordination geometry of 1 is intermediate between the trigonal pyramidal and seesaw shapes insofar as each Hg(II) is four-coordinate and 2-pyimiso is a monodentate ligand. X-ray structure and Hirshfeld surface analyses have revealed that the supramolecular arrangement of 1 comprises perpendicular 1-D chains along the [011] direction assembled by nonclassical C–H?Cl–Hg and C–H?π hydrogen bonds. Moreover, adjacent sheets parallel to the bc-plane are interconnected by C–H?N_py, π–π_py stacking, and Hg?π_py interactions.     

The structure of β-diketones related to curcumin determined by X-ray crystallography,NMR (solution and solid state) and theoretical calculations

Structural Chemistry - Structural data are reported on sixteen ketoenols of β-diketones: solution NMR, solid-state NMR (CPMAS and MAS) and X-ray crystallography (four compounds, where three...     

Synthesis,crystal structure and DFT calculations of octahedral nickel(II) complexes derived from N′-[(E)-phenyl(pyridin-2-yl)methylidene]benzohydrazide

The two new nickel(II) complexes, [Ni(HL)(L)](NO₃)?H₂O (1) and [Ni(L)₂] (2) (where HL/L = N′-[(E)-phenyl(pyridin-2-yl)methylidene]benzohydrazide), have been synthesized and characterized by elemental analysis, spectroscopic, magnetic susceptibility, and cyclic voltammetric measurements. Single-crystal X-ray analysis of [Ni(HL)(L)](NO₃)?H₂O (1) and [Ni(L)₂] (2) has revealed the presence of a distorted octahedral geometry around nickel(II). The X-ray and spectral characterizations have confirmed the existence of the keto-enol form of the ligands in the complexes. The electronic structures and spectral properties of the ligands and the complexes have been explained by DFT and TDDFT calculations. Superoxide dismutase activity of these complexes has also been measured.     

Spectroscopic characterizations on the N,N′-bis-alkyl derivatives of 1,4,6,8-naphthalenediimide charge-transfer complexes

Charge-transfer (CT) complexes formed from the reactions of two N,N′-bis-alkyl derivatives of 1,4,6,8-naphthalenediimide such as N,N′-bis-[2-hydroxyethyl]-1,4,6,8-naphthalenediimide (BHENDI) and N,N′-bis-[2-N,N-dimethylaminoethyl]-1,4,6,8-naphthalenediimide (BDMAE NDI) with DDQ, CHL, TCNQ, DCQ and DBQ as π-acceptors have been studied spectrophotometrically in chloroform and/or methanol at 25 °C. The photometric titration curves for the reactions indicated that the data obtained refer to 1:1 charge-transfer complexes of [(BHENDI)(DDQ)], [(BDMAENDI)(DDQ)], [(BHENDI)(CHL)], [(BDMAENDI)(CHL)], [(BHENDI)(TCNQ)], [(BDMAENDI)(TCNQ)], [(BHENDI)(DCQ)], [(BDMAENDI)(DCQ)], [(BHENDI)(DBQ)] and [(BDMAENDI)(DBQ)] were formed. Benesi–Hildebrand and its modification methods were applied to the determination of association constant (K), molar extinction coefficient (?). The solid CT complexes have been synthesized and characterization by different spectral methods.