B3PW91 Levels Research Articles

Oxygen Atom Transfer to Cationic PCPNi(II) Complexes Using Amine-N-Oxides.

Three PCsp3P pincer ligands differing in the aryl group linking the phosphine arms with the anchoring carbon donor were used to support square planar Ni(II) bromide complexes 1-3Br. Exchange of the coordinating bromide anion for the more weakly coordinating triflate (OTf) or hexafluoroantimonate (SbF6) anions was accomplished by treatment with AgX or TlX salts to give compounds 1-3X; compounds 1OTf, 1SbF6, 2Br, 2OTf, 3Br, and 3SbF6 were all characterized by X-ray crystallography. The reactions of these Ni(II) compounds with the amine-N-oxide oxygen atom transfer agents ONMe3 and ONMePh2 were explored. For ONMe3, reactions with 2 equiv gave products in which one arm of the pincer ligand was oxidized to a P═O unit, with the other amine-N-oxide ligated to the Ni(II) center, forming products 5-6X; compounds 4OTf, 5OTf, and 6SbF6 were characterized crystallographically. Transient amine-N-oxide adducts prior to ligand oxidation were observed in some reactions. For the more effective O atom donor ONMePh2, reactions were very rapid and a second oxidation of the remaining phosphine arm was observed, producing a Ni(II) species with an OCO pincer ligand (7SbF6). All compounds were fully characterized. Experiments aimed at trapping transient Ni(IV) oxo intermediates (with cyclohexadiene, KH, and various Lewis acids) indicated that such species were not involved in the reaction. This was supported by density functional theory (DFT) computations at the B3PW91 level, which indicated that direct O atom insertion into the Ni-P bonds without the intermediacy of a Ni oxo species was the low-energy pathway.

Exploring the activities of vanadium, niobium, and tantalum PNP pincer complexes in the hydrogenation of phenyl-substituted CN, CN, CC, CC, and CO functional groups

The structures and stability of the designed PNP pincer amido M(NO) 2 (PNP) and amino H M(NO) 2 (PN H P) complexes [M = V, Nb, and Ta, PNP = N(CH 2 CH 2 P(isopropyl) 2 ) 2 , PN H P = HN(CH 2 CH 2 P(isopropyl) 2 ) 2 ] and their hydrogenation mechanisms for phenyl-substituted unsaturated functional groups have been explored at the B3PW91 level of density functional theory. Under H 2 environment, these conjugated complexes can form equilibrium and fulfill the criteria of metal–ligand cooperated bifunctional hydrogenation catalysts. For the hydrogenation of Ph-C N, Ph-CH NH, Ph-CH NH-Ph, Ph-CH N CH 2 Ph, Ph-C CH, Ph-CH CH 2 , Ph-CHO, and Ph-CO CH 3 , the reaction prefers either a two-step or one-step mechanism for the hydridic M H and protonic N H transfer. These results clearly show that the V, Nb, and Ta complexes are promising catalysts for the hydrogenation reactions, and these provide experimental challenges.

Investigating solvent effects on aggregation behaviour, linear and nonlinear optical properties of silver nanoclusters

We herein report the solvent effects on the aggregation, linear and nonlinear optical properties of silver nanoclusters synthesised using three solvents namely; ethanol, acetone and isopropanol. The Ag clusters were characterized using UV–Visible (UV–vis) and photoluminescence (PL) spectroscopy, Fourier transform-infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), small angle X-ray scattering (SAXS), dynamic light scattering (DLS), and open aperture Z-Scan measurements. Density functional theory (DFT) calculations at the B3PW91 level of theory, were done to compute the electric dipole, quadrupole, octapole and hexadecapole moment of mercaptosuccinic acid and mercaptosuccinic acid-Ag9 cluster in three solvents. Linear optical properties show characteristic absorption profile with quantum confinement at different wavelengths for all the three clusters. The Open aperture Z-scan measurement in Ag clusters establishes the optical limiting properties which arise mostly from excited state absorption (ESA) and relatively weak saturable absorption (SA). The nonlinear optical behaviour varies within the three clusters with maximum optical limiting value obtained for the clusters synthesised using acetone. The theoretically computed hyperpolarizabilities together with z-scan measurements establish the solvent effect on the clusters and their potential applications in optical limiting devices.

Spectroscopic, optical, DNA, antimicrobial and density functional theory studies of 5-Bromo-2-(trifluoromethyl)pyridine

The spectroscopic characterization of 5-Bromo-2-(trifluoromethyl)pyridine was performed by the applying of Fourier Transform-Infrared (FT-IR) and 1H and 13C Nuclear Magnetic Resonance (NMR) spectroscopies. The optimized geometric structure of 5-Bromo-2-(trifluoromethyl)pyridine was searched by density functional theory (DFT) on employing B3LYP, CAMB3LYP, and B3PW91 functional. The vibrational frequencies and chemical shift values were calculated by using B3LYP, CAMB3LYP, and B3PW91 levels with the 6–31++G(d, p) basis set. The non-linear optical (NLO) properties of 5-Bromo-2-(trifluoromethyl)pyridine were determined using the same methods The HOMO-LUMO energies were examined by applying time-dependent DFT (TD-DFT) method with integral equation formalism-polarized continuum model (IEF-PCM). The second-order interaction energies of the title molecule were derived from Natural Bond Orbital (NBO) analysis. The effect of the molecule on pBR322 plasmid DNA was monitored by agarose gel electrophoresis experiments. The antimicrobial activities were tested by using minimal inhibitory concentration method (MIC).

Phosphate functionalized (4,4)-armchair CNTs as novel drug delivery systems for alendronate and etidronate anti-osteoporosis drugs

The ability of (4,4)-armchair CNT and its three phosphate functionalized forms (CNT-nH2PO4, n=1–3) were evaluated as novel drug delivery systems (DDSs) for the two commercially well-known anti-osteoporosis drugs namely alendronate (AL) and etidronate (ET). For this purpose, the DFT calculations were accomplished at both B3LYP and B3PW91 levels using 6–31g(d) basis set. The binding energy was increased by increasing number of H2PO4 moieties attached on the CNT with the most negative binding energy was measured for the carrier containing three phosphate groups. The dipole moments of all phosphate containing CNTs were much greater (∼2.2–4.4D) than that of pristine CNT (∼0D). The contour maps proved that when the CNT was functionalized by H2PO4 groups, the symmetric distribution of electric charge was vanished with the charge distribution was the highest asymmetric for the CNT-2H2PO4 while it was the lowest asymmetric for CNT-3H2PO4 leading to the greatest dipole moment for the CNT-2H2PO4 (4.177D) while the smallest dipole moment for the CNT-3H2PO4 (1.614D). Among all compounds, those containing the CNT-3H2PO4 exhibited the smallest band gap energy, chemical potential and hardness but the greatest electronegativity and electrophilicity index which were all suitable and effective for the attachment of drugs onto the bone surface (having partial positive charge due to the presence of Ca2+ as CaCO3) and therefore inhibiting the osteoporosis. Consequently, it was established that the drug-CNT-3H2PO4 was the most appropriate drug-carrier compound for both of the AL and ET drugs and it could be used as the most effective drug vehicle. The attachment of AL, ET drugs as well as the AL-CNT-3H2PO4 and ET-CNT-3H2PO4 drug-carrier systems to the bone tissue was modelled by optimization of the structures of these compounds bonded to the hydroxyapatite (HA)-17water (w). It was found that among these four systems, the AL-CNT-3H2PO4 could be suggested as the most suitable DDS for application in the treatment of osteoporosis.

Synthesis, crystal structure, spectroscopic characterization and theoretical calculations of (Z)-N-(naphthalen-2-yl)-1-(5-nitrothiophen-2-yl)methanimine

The newly synthesized Schiff base compound, (Z)-N-(naphthalen-2-yl)-1-(5-nitrothiophen-2-yl)methanimine, C15H10N2O2S, was characterized by IR, UV–Vis and X-ray diffraction technique. All of the theoretical calculations have been calculated at the LSDA, BVP86, B3LYP and B3PW91 levels of the density functional method (DFT) with the 6–311++G(d,p) basis set by Gaussian software. UV–Visible absorption spectra of the title compound dissolved in ethanol were recorded and computed using the time dependent density functional theory (TD-DFT). The harmonic vibrational frequencies of the title compound were calculated using the same methods. So as to determine most favorable conformation as theoretically, molecular energy profile of the title compound were obtained as a function of the selected torsion angle by steps of 10° in the range of −180° to +180° rotation around the bond. The conformational analysis is a relationship between the energy of the title compound and its geometry. It is demonstrated that comparison between the calculated and experimental results provide a very good agreement. The energetic behavior such as the total energy, atomic charges, dipole moment of the title compound in solvent media were examined using the same methods by applying the Onsager and the integral equation formalism polarizable continuum model (IEF-PCM).

Synthesis, crystal structure, spectroscopic investigations and DFT calculations of the copper(II) complex of 4-(Trifluoromethyl)pyridine-2-carboxylic acid

A novel polymeric complex of Cu(II) ion, [Cu(tfpc)2]n [tfpc: 4-(Trifluoromethyl)pyridine-2-carboxylate] has been prepared and characterized spectroscopically (by FT-IR) and structurally (by single-crystal XRD). The geometry around the Cu(II) center can be described as square planar made by tfpc ligand having nitrogen and oxygen atoms. Additionally, the Cu(II) complex has a one-dimensional double-bridged polymeric structure in which Cu(II) ions are bridged by two oxygen atoms of adjacent planes. The crystal packing has been stabilized by CH⋯O intra and intermolecular hydrogen bonds. The molecular structure of the Cu(II) complex has been optimized using the Density Functional Theory (DFT) B3LYP, B3PW91 and PBEPBE levels with 6-311+G(d,p) basis set. The calculated electronic spectra have been explained using the time dependent DFT (TD-DFT) method by applying the polarized continuum model (PCM). The vibrational spectral data have been calculated and compared with experimental ones. The non-linear optical (NLO) properties of the title compound have been investigated using the DFT method with three different levels. Natural Bond Orbital (NBO) property of the Cu(II) complex has been performed by the B3LYP density functional and the 6-311+G(d,p) basis set.

A Theoretical Investigation of the Decomposition and Reactivity of the CHF2CF2CF2OCH2O• Radical from HFE-356pcc3 between 200 and 400 K

This investigation involves the ab initio quantum mechanical study of the decomposition and reactivity of the CHF2CF2CF2OCH2O• radical that is formed from CHF2CF2CF2OCH3(HFE-356pcc3). The geometries of the reactants, products and transition states were optimised at the B3LYP and B3PW91 levels of theory using the 6-311G(d,p) basis set. Five important pathways for the decomposition and reactivity of CHF2CF2CF2OCH2O• were investigated: (1) reaction with atmospheric O2, (2) reaction with atmospheric •OH radical, (3) C–O bond cleavage, (4) H elimination and (5) the migration of hydrogen from carbon to oxygen and then C–O bond cleavage, with energy barriers of 4.4 (5.0), 11.9 (12.4), 17.0 (17.3), 20.4 (19.4) and 32.2 (32.6) and 15.5 (16.7) kcal mol−1respectively [values in parentheses are for the B3PW91/6-311G(d,p) level of theory].Rate constants were calculated by utilising canonical transition state theory in the range 200–400 K and the corresponding Arrhenius diagrams have been plotted. The results showed that the rates of decomposition and reaction increase with increasing temperature. Also, between 200 and 306 K, path (1) has the highest rate constant: moreover, it was concluded that reaction with atmospheric O2is the dominant pathway for the consumption of CHF2CF2CF2OCH2O• in the atmosphere. An intrinsic reaction coordinate calculation was performed to confirm the existence of a transition state on the corresponding potential energy surface.

DFT computational study on the phosphate functionalized SWCNTs as efficient drug delivery systems for anti-osteoporosis zolendronate and risedronate drugs

The pristine (4,4)-armchair SWCNT as well as its three phosphate functionalized (CNT-nH2PO4, n=1–3) forms were studied as novel drug delivery systems for the two commercially famous anti-osteoporosis drugs including risedronate (RIS) and zolendronate (ZOL) using the density functional theory (DFT) computations at both B3LYP and B3PW91 levels. Results revealed that the binding energy was increased by increasing number of H2PO4 moieties attached on the CNT with the most negative binding energy was measured for the CNT-3H2PO4 carrier. The dipole moments of all phosphate containing CNTs were much greater (~1.5–4.5D) than that of pristine CNT (~0D). The contour maps verified that when the CNT was functionalized by H2PO4 groups, the symmetric distribution of electric charge was vanished so that the highest and the lowest asymmetric charge distributions were achieved for the CNT-2H2PO4 and CNT-3H2PO4, respectively, leading to the greatest and the smallest dipole moments for the CNT-2H2PO4 (4.177D) and the CNT-3H2PO4 (1.614D). The compounds RIS-CNT-3H2PO4 and ZOL-CNT-3H2PO4 displayed the greatest electronegativity and electrophilicity index which were appropriate for the binding of drugs onto the bone surface (having partial positive charge due to the presence of Ca2+) and therefore effectively inhibiting the osteoporosis. Consequently, it was proposed that the drug-CNT-3H2PO4 was the most appropriate drug-carrier system for both of the RIS and ZOL drugs which could be employed as the most efficient vehicle.

A comparative study of oxygen-doped and pure beryllium clusters based on structural, energetic and electronic properties

The lowest-energy structures of the oxygen-doped Ben (n=1–12) clusters are obtained at the B3PW91 level. Various energetic and electronic properties of the BenO clusters are systematically investigated using the QCISD(T) method, which are compared with those of pure Ben+1 clusters. The evolution of these properties with cluster size shows the unique stability of Be11O, which can actually be considered as an ionic compound (Be11)2+O2−. On the one hand, O2− has 8 valence electrons, satisfying the octet rule. On the other hand, the Be112+ moiety has a shell-closed electronic configuration, which renders itself particularly stable.

Effect of ionic charge on O[formula omitted]H⋯Se hydrogen bond: A computational study

Complexes between para-substituted cationic phenol and SeH2 have been investigated in electronic ground state at the B3LYP, B3PW91, and ωB97xD levels of theory using 6-311++G(3df,3pd) basis set. Various electron-donating and withdrawing substituents (NH2, OH, CH3, H, F, Cl, CN, and NO2) are used to characterize electronic substituent effect on intermolecular +OH⋯Se hydrogen bond. Electron withdrawing substituent increases hydrogen bond stabilization energy and red shift in OH stretching frequency. Introduction of a positive charge transforms weak hydrogen bond of neutral OH⋯Se type into a strong hydrogen bond. Complexation induced changes on various hydrogen bond parameters, such as, stabilization energy, change in OH bond length, change in OH stretching frequency, extent of charge transfer from hydrogen bond acceptor to donor, hydrogen bond orders, electron density at the hydrogen bond critical point exhibit conventional electronic substitution effect. Stabilization energy of +OH⋯Y hydrogen bond are similar in the complexes between cationic phenol and SH2/SeH2, whereas it is almost twice with OH2 in case of +OH⋯Y hydrogen bond.

Comparison of different hybrid DFT methods on structural, spectroscopic, electronic and NLO parameters for a potential NLO material

The molecular geometrical, vibrational frequency, molecular static polarizability and hyperpolarizability parameters, as well as HOMO-LUMO energies of 4-Aminopyridinium monophthalate (4-APMP) as potential nonlinear optical (NLO) material in the ground state were examined using hybrid GGA, meta-GGA, range-separated hybrid and long-range (LR) corrected models (B3LYP, B3PW91, M062X, HSEh1PBE, CAM-B3LYP, LC-BLYP and ωB97XD levels of density functional theory) with 6-311G(d,p) basis set in order to analyze the effects of different percentage of HF exchange. TD-DFT computations with the PCM (polarizable continuum model) within methanol solvent based on implicit/explicit model and gas phase in the excited state were employed to investigate UV–vis absorption and fluorescence emission wavelengths. Furthermore, by regarding the potential energy distribution (PED), a detailed vibrational study was fulfilled by using VEDA program. Experimental values of structural and spectroscopic parameters of 4-APMP were used to display the effects of the different theoretical methods on the spectroscopic and structural properties. To display the agreement and accuracy of among selected DFT levels and experimental data, the linear correlation coefficients (R2), mean absolute deviation (MAD), overall mean percent deviation (MPD), optimal scaling factor (λ) and overall root mean square (RMS) deviation for structural and vibrational frequency parameters were presented. The NLO parameters indicated that 4-APMP exhibits significant molecular nonlinearity.

Computational study of the threshold energy for the 1,2-interchange of X and R (X, R = halogens, pseudohalogens, and monovalent hydrocarbon groups) on CH2XCH2R

Transition state geometries and threshold energies, E0, were computed for an unusual unimolecular isomerization reaction that exchanges two groups (X, R) on CH2XCH2R. An objective is to determine the most energetically feasible interchanges to guide experimental investigations. The interchanging species included halogens (F, Cl, Br) and pseudohalogens and monovalent hydrocarbons (H, SH, CH3, NH2, OH, OCF3, OCH3, CH=CH2, CH2CH3, CH2OH, C≡CH, CH2CF3, CCl3, CF3) attached to a two carbon backbone. Ground state and transition state geometries were optimized with the B3PW91 level of theory and 6-311+G(2d,p) basis set. The Br–Br interchange had the lowest E0 (141 kJ/mol), and CH3–H had the highest E0 (582 kJ/mol). In general, larger atoms or groups with lone pairs of electrons such as halogens, SH, OH, OCH3, OCF3, and NH2 tend to lower the E0 barrier for interchange, making them the most likely to be experimentally observed.

Dispersion Forces, Disproportionation, and Stable High-Valent Late Transition Metal Alkyls.

The transition metal tetra- and trinorbornyl bromide complexes, M(nor)4 (M=Fe, Co, Ni) and Ni(nor)3 Br (nor=1-bicyclo[2.2.1]hept-1-yl) and their homolytic fragmentations were studied computationally using hybrid density functional theory (DFT) at the B3PW91 and B3PW91-D3 dispersion-corrected levels. Experimental structures were well replicated; the dispersion correction resulted in shortened M-C bond lengths for the stable complexes, and it was found that Fe(nor)4 receives a remarkable 45.9 kcal mol-1 stabilization from the dispersion effects whereas the tetragonalized Co(nor)4 shows stabilization of 38.3 kcal mol-1 . Ni(nor)4 was calculated to be highly tetragonalized with long Ni-C bonds, providing a rationale for its current synthetic inaccessibility. Isodesmic exchange evaluation for Fe(nor)4 confirmed that dispersion force attraction between norbornyl substituents is fundamental to the stability of these species.

CO2 adsorption on the surface and open ended of Single wall carbon nanotubes (SWCNTs): A Comparative study

Adsorption of CO2 on the surface of Single-wall zigzag (5,0) and armchair (4,4) carbon nanotubes (SWCNTs) were studied through using density functional theory (DFT) calculations. Optimizations of geometric were performed at the B3PW91 level of 6-311++G** method standard basis set using GAUSSIAN 03 package of program [1]. Structural models were optimized and adsorption energies, band gap, charge transfer and dipole momentum were obtained to investigate the nuclear magnetic resonance (NMR) and Nuclear Quadrupole Resonance (NQR) spectroscopy parameters for (CO2-CNTs) model of zigzag (5,0) and armchair (4,4) SWCNTs. Comparison of the results of the zigzag and armchair models with calculated chemical shielding, electric filed gradient tensors at the sites of carbon on the Surface and open ended revealed that CO2 adsorption has a dramatic effect on the electronic structure of SWCNTs and the more adsorption on the surface is about -1.5747eV SWCNT-S (5, 0) nanotube.

DFT computations on the hydrogen bonding interactions between methacrylic acid-trimethylolpropane trimethacrylate copolymers and letrozole as drug delivery systems

The hydrogen bonding interactions between letrozole (Let) anticancer drug and three copolymers of methacrylic acid-trimethylolpropane trimethacrylate (M1–M3 as molecular imprinted polymers) were studied using density functional theory (DFT) at both B3LYP and B3PW91 levels. The binding energies were corrected for the basis set superposition error (BSSE) and zero-point vibrational energies (ZPVE) so that the most negative [Formula: see text] were measured for compounds 7 and 8 formed between M1 copolymer and endocyclic N1 and N2 atoms of drug, respectively. Also, among complexes 13–15 in which two copolymers were contributed in the formation of O–H[Formula: see text]N bonds with the drug, compound 13 (containing two M1 copolymers) showed the highest [Formula: see text] value. The interactions of all copolymers with drug were exergonic (spontaneous interaction) and exothermic. The QTAIM data supported the covalent character of the C–N, C–H, N–N, C–O, O–H and O–H[Formula: see text]N bonds, the intermediate nature of C[Formula: see text]N and C[Formula: see text]O bonds while the electrostatic character of C–H[Formula: see text]O, HC[Formula: see text]HC and CH[Formula: see text]N interactions. According to the [Formula: see text], [Formula: see text] and [Formula: see text] values, it was suggested that t complexes 7 and 8 (among two particles systems) as well as complex 13 (among three particles systems) can be the most promising drug delivery systems.

Crystal structure, spectroscopic investigations and quantum chemical computational study of 5-(diethylamino)-2-((3-nitrophenylimino)methyl)phenol

The Schiff base compound, 5-(diethylamino)-2-((3-nitrophenylimino)methyl)phenol, C17H19O3N3, was synthesized and characterized by IR, UV–Vis and single-crystal X-ray diffraction (XRD) technique. The title compound prefers enol tautomeric form in solid state as to X-ray, IR and UV–Vis spectra results. Also, using the TD-DFT method, the electronic absorption spectra of the title compound was computed in both the gas phase and ethanol solvent. The calculated results support that the enol form is more stable than keto form. The molecular geometry from the X-ray single-crystal determination of the title compound in the ground state was compared at the B3LYP and B3PW91 levels of the density functional method (DFT) with the 6-311 + G(d,p) basis set. The harmonic vibrational frequencies of the title compound were calculated using the B3LYP and B3PW91 methods with the 6-311G+(d,p) basis set. The calculated results were compared with the experimental determination results of the compound. The potential energy surface scans about important torsion angels were performed by B3LYP/6-311 + G(d,p) level of theory for the title compound. The energetic behaviors of the title compound in the solvent media were also examined using the B3LYP and B3PW91 methods with the 6-311 + G(d,p) basis set applying the Onsager and the polarizable continuum model (PCM). Besides, the molecular electrostatic potential map (MEP), frontier molecular orbitals (FMO) analysis and thermodynamic properties for the title compound were obtained with the same levels of theory. The nonlinear optical properties (NLO) of the title compound were performed in the solvent media using the B3LYP and B3PW91 methods with the 6-311 + G(d,p) level using the PCM model.

Geometries, stabilities, electronic and magnetic properties of small aluminum cluster anions doped with cobalt: A density functional theory study

The geometrical structures, relative electronic and magnetic properties of small Al n Co– (1 ≤ n ≤ 9) clusters are systematically investigated within the framework of density functional theory at the BPW91 level. The single Co doping can dramatically affect the ground state geometries of the 1 Al n+1 - clusters. At the same time, the resulting geometries show that the lowest energy Al n Co– clusters prefer to be three dimensional structures. Here, the relative stabilities are investigated in terms of the calculated average binding energies, fragmentation energies, and second-order energy differences. Moreover, the result of the highest occupiedlowest unoccupied molecular orbital energy gaps indicates that Al6Co– clusters have the highest chemical stability for Al n Co– (1 ≤ n ≤ 9) clusters. Furthermore, the natural population analysis reveals that the charges in Al n Co– clusters transfer from the Al frames to the Co atom. Additionally, the analyses of the local and total magnetic moments of the Al n Co– clusters show that the magnetic effect mainly comes from the Co atom.

Density functional efficiency in the calculations of vibrational frequencies and molecular structures of β-diketones

Density functional theory (DFT) levels are employed to calculate the vibrational frequencies and geometrical data of β-diketones. We evaluate the relative performance of the different levels by comparing theoretical results to experimental values. The applied DFT levels in this work are B3LYP, BLYP, B3P86, B3PW91, BPW91, G96LYP, BP86, and G96PW91 with the standard 6-31G, 6-31G*, 6-31G**, 6-31+G**, 6-31++G**, 6-311G**, 6-311++G** basis sets. The best results are obtained at the B3LYP, B3PW91, and B3P86 levels.

Structural and spectral properties of tartrato complexes of vanadium(V) from quantum chemical calculations

Structural and spectral properties of three complex anions of vanadium(V) with tartrato ligands were theoretically studied by all-electron DFT calculations employing various functionals, such as BP86, BLYP, B3LYP, BHHLYP, and the M06-family. Results were statistically evaluated, with the aim to find a reliable, fairly accurate, and yet computationally efficient combination of methods and basis sets to be used in computational chemistry of vanadium(V) complex anions at even larger scale. Subsequent vibrational analysis based upon BP86 and B3LYP data provided a fair agreement with the experimental vibrational spectra. Additionally, the absorption UV–Vis and the electronic circular dichroism spectra of studied compounds were simulated via time-dependent density functional theory calculations with the long-range corrected functionals (CAM-B3LYP, LC-ωPBE, and ωB97XD). Finally, the 51V NMR chemical shifts were calculated using the GIAO approach at the B3PW91 level. The solvent effect was simulated within the PCM model. Where available, the calculated spectral properties were compared with experimental data.