Excited-state hydrogen bonding and deprotonation of esculetin in solution: a DFT/TDDFT study

The combined density functional theory (DFT) and time-dependent density functional theory (TDDFT) method was used to study the electronic spectral properties of different deprotonated forms of esculetin. By comparing the experimental absorption and fluorescence bands with the calculated electronic spectra, it is evidently demonstrated that the minor absorption and fluorescence bands observed at slightly longer wavelengths than the principal bands in experiments are predominantly from the de-H3 form of the esculetin monomer. Furthermore, we clarified the relationship between electronic spectral shifts and electronic excited-state intramolecular hydrogen bonding changes: the strengthening of intramolecular hydrogen bond can induce an electronic spectral blueshift while the intramolecular hydrogen bond weakening can result in an electronic spectral redshift.     

Water exchange in fluoroaluminate complexes in aqueous solution: a variable temperature multinuclear NMR study

An 17O, 19F, and 27Al NMR study of fluoroaluminate complexes (AlFn(H2O)6-n((3-n)+), n = 0, 1, and 2) in aqueous solution supports the idea that for each substitution of a bound water molecule by a fluoride anion, the exchange rate of bound water with free water increases by about 2 orders of magnitude. New rate coefficients for exchange of inner-sphere water molecules in AlF(H2O)5(2+) are kex(298) = 230(+/-20) s(-1), DeltaH(dagger) = 65(+/-3) kJ mol(-1), and DeltaS(dagger) = 19(+/-10) J mol(-1) K(-1). The corresponding new values for the AlF2(H2O)4(+) complex are: kex(298) = 17 100(+/-500) s(-1), DeltaH(dagger) = 66(+/-2) kJ mol(-1), and DeltaS(dagger) = 57(+/-8) J mol(-1) K(-1). When these new results are combined with those of our previous study,(4) we find no dependence of the solvent exchange rate, in either AlF(H2O)5(2+) or AlF2(H2O)4(+), on the concentration of fluoride or protons over the range of SigmaF = 0.06-0.50 M and [H(+)] = 0.01-0.44 M. A paramagnetic shift of 27Al resonances results from addition of Mn(II) to the aqueous solution as a relaxation agent for bulk waters. This shift allows resolution of the AlFn(H2O)6-n((3-n)+) species in 27Al NMR spectra and comparison of the speciation determined via thermodynamic calculations with that determined by 27Al, 19F, and 17O NMR.     

NMR spectra of salicylohydroxamic acid in DMSO-d6 solution: a DFT study

The ¹H, ¹³C and ¹H, ¹³C COSY NMR spectra of salicylohydroxamic acid (sha) were measured in DMSO-d₆ solution. The B3LYP GIAO method with the 6-311++G(d,p) basis set was chosen to reproduce the experimental spectra. All possible zusammen and entgegen conformers of monomeric sha were computed. After geometry optimisation (B3LYP/6-311++G(d,p)) only nine independent models of the molecule were shown to be stable. Additionally, the NMR chemical shifts of the Onsager model of the most stable monomer were calculated. The computed chemical shifts for the labile protons for all aforementioned geometries meaningfully underestimated experimental results suggesting the existence of the H-bonded structure of sha in DMSO solution. The most probable two dimeric structures along with two solvent-bounded aggregates were subsequently calculated at the same level of theory. The best agreement was obtained for sha H-bonded with two DMSO molecules (confirmed by the absence of concentration effect). The relative error not exceeding 10 and 4% for chemical shifts in ¹H and ¹³C NMR spectra of sha–(DMSO)₂, respectively, showed that the applied method with the B3LYP/6-311++G(d,p) basis set was efficient to predict the NMR shifts of a compound with strong H-bonds. Thus, this allows to assign properly NMR resonances to specific structure formed in DMSO solution.     

Solution chemistry of uranyl ion with iminodiacetate and oxydiacetate: A combined NMR/EXAFS and potentiometry/calorimetry study

The solution chemistry of uranyl ion with iminodiacetate (IDA) and oxydiacetate (ODA) was investigated using NMR and EXAFS spectroscopies, potentiometry, and calorimetry. From the NMR and EXAFS data and depending on stoichiometry and pH, three types of metal:ligand complex were identified in solution in the pH range 3-7: 1:1 and 1:2 monomers; a 2:2 dimer. From NMR and EXAFS data for the IDA system and previous studies, we propose the three complex types are [UO(2)(IDA)(H(2)O)(2)], [UO(2)(IDA)(2)](2)(-), and [(UO(2))(2)(IDA)(2)(mu-OH)(2)](2)(-). From EXAFS spectroscopy, similar 1:1, 2:2, and 1:2 complexes are found for the ODA system, although (13)C NMR spectroscopy was not a useful probe in this system. For the 1:1 and 1:2 complexes in solution, EXAFS spectroscopy is ambiguous because the data can be fitted with either a long U-N/O(ether) value (ca. 2.9 A) suggesting 1,7-coordination of the ligand or a U-C interaction at a similar distance, consistent with terminal bidentate coordination. However, the NMR data of the IDA system suggest that 1,7-coordination is the more likely. The stability constants of the three complexes were determined by potentiometric titrations; the log beta values are 9.90 +/-, 16.42 +/-, and 10.80 +/- for the 1:1, 1:2, and 2:2 uranyl-IDA complexes, respectively, and 5.77 +/-, 7.84 +/-, and 4.29 +/- for the 1:1, 1:2, and 2:2 uranyl-ODA complexes, respectively. The thermodynamic constants for the complexes were calculated from calorimetric titrations; the enthalpy changes (kJ mol(-)(1)) and entropy changes (J K(-)(1) mol(-)(1)) of complexation for the 1:1, 1:2, and 2:2 complexes respectively are the following. IDA: 12 +/- 2, 230 +/- 8; 8 +/- 2, 151 +/- 9; -33 +/- 3, -283 +/- 11. ODA: 26 +/- 2, 198 +/- 12; 20 +/- 2, 106 +/- 8; -24 +/- 2; -219 +/- 8.     

Stabilization of a subvalent oxidation state of bismuth in N,N-dimethylthioformamide solution: an EXAFS, UV-Vis, IR, and cyclic voltammetry study

At the dissolution of anhydrous bismuth(III) trifluoromethanesulfonate in N,N-dimethylthioformamide (DMTF) a deep red-orange complex, lambda(max) = 457 nm, is formed. Bismuth(III) is reduced by the solvent to a low-valent oxidation state stabilized by the sulfur-coordinating solvent DMTF. The obtained complex is weakly solvated seen by a low EXAFS amplitude and a slightly higher absorption energy of the L(III) edge than of the DMTF-solvated bismuth(III) ion. The EXAFS data reveal a dimeric bismuth complex solvated by a single DMTF molecule, which sulfur atom bridges the bismuth atoms. The Bi-S bond distance is 2.543(2) A, and the Bi...Bi distance is 3.929(7) A giving a Bi-S-Bi angle of 101.2(4) degrees. The very low number of coordinated solvent molecule shows that the lone electron pairs of the reduced bismuth ions are stereochemically active. Cyclic voltammetry investigations provide evidence that at least one bismuth atom in the dimer exists in an oxidation state lower than +III, seen by two peaks at approximately -0.36 and -0.57 V in the reduction half-cycle. The absence of EPR signals excludes the presence of bismuth(II) radicals.     

Solution equilibria of aromatic dinitroso compounds: a combined NMR and DFT study

Solution-state nitroso monomer-azodioxide equilibria and conformational freedom of several aromatic dinitroso derivatives, differing in the spacer group between the aromatic rings, were studied by one- and two-dimensional variable temperature ¹H NMR spectroscopy and by quantum chemical calculations. The proton signals of nitroso monomer-azodioxide mixtures revealed by low-temperature NMR were assigned and validated using B3LYP-D3/6-311+G(2d,p)/SMD level of theory. In almost all cases, a preference towards the formation of only one azodioxy isomer of aromatic dinitroso compounds was found, which was assigned to Z-dimer according to computational data. Nevertheless, the computed small energy difference between the Z- and E-isomer could not account for the extreme preference for Z-dimer formation, indicating an influence of entropic or solvent effects. The formation of shorter oligomers in solution was excluded based on integrated ¹H NMR signal intensities. The experimental results indicated an average dimerization Gibbs energy of about ??5 kJ/mol at 223 K and were found to be in very good correlation with dimerization energies obtained by solution-phase optimization.

     

The structure of the chiral Pt531 surface: a combined LEED and DFT study

The structure of the chiral kinked Pt531 surface has been determined by low-energy electron diffraction intensity-versus-energy (LEED-IV) analysis and density functional theory (DFT). Large contractions and expansions of the vertical interlayer distances with respect to the bulk-terminated surface geometry were found for the first six layers (LEED: d12 = 0.44 A, d23 = 0.69 A, d34 = 0.49 A, d45 = 0.95 A, d56 = 0.56 A; DFT: d12 = 0.51 A, d23 = 0.55 A, d34 = 0.74 A, d45 = 0.78 A, d56 = 0.63 A; dbulk = 0.66 A). Energy-dependent cancellations of LEED spots over unusually large energy ranges, up to 100 eV, can be explained by surface roughness and reproduced by applying a model involving 0.25 ML of vacancies and adatoms in the scattering calculations. The agreement between the results from LEED and DFT is not as good as in other cases, which could be due to this roughness of the real surface.     

Effects of benzoannulation and alpha-octabutoxy substitution on the photophysical behavior of nickel phthalocyanines: a combined experimental and DFT/TDDFT study

The photophysical properties of a group of Ni(II)-centered tetrapyrroles have been investigated by ultrafast transient absorption spectrometry and DFT/TDDFT methods in order to characterize the impacts of alpha-octabutoxy substitution and benzoannulation on the deactivation pathways of the S1(pi,pi*) state. The compounds examined were NiPc, NiNc, NiPc(OBu)8, and NiNc(OBu)8, where Pc = phthalocyanine and Nc = naphthalocyanine. It was found that the S1(pi,pi*) state of NiNc(OBu)8 deactivated within the time resolution of the instrument (200 fs) to a vibrationally hot T1(pi,pi*) state. The quasidegeneracy of the S1(pi,pi*) and 3(dz2,dx2-y2) states allowed for fast intersystem crossing (ISC) to occur. After vibrational relaxation (ca. 2.5 ps), the T1(pi,pi*) converted rapidly (ca. 19 ps lifetime) and reversibly into the 3LMCT(pi,dx2-y2) state. The equilibrium state, so generated, decayed to the ground state with a lifetime of ca. 500 ps. Peripheral substitution of the Pc ring significantly modified the photodeactivation mechanism of the S1(pi,pi*) by inducing substantial changes in the relative energies of the S1(pi,pi*), 3(dpi,dx2-y2), 3(dz2,dx2-y2), T1(pi,pi*), and 1,3LMCT(pi,dx2-y2) excited states. The location of the Gouterman LUMOs and the unoccupied metal level (dx2-y2) with respect to the HOMO is crucial for the actual position of these states. In NiPc, the S1(pi,pi*) state underwent ultrafast (200 fs) ISC into a hot (d,d) state. Vibrational cooling (ca. 20 ps lifetime) resulted in a cold (dz2,dx2-y2) state, which repopulated the ground state with a 300 ps lifetime. In NiPc(OBu)8, the S1(pi,pi*) state deactivated through the 3(dz2,dx2-y2), which in turn converted to the 3LMCT(pi,dx2-y2) state, which finally repopulated the ground state with a lifetime of 640 ps. Insufficient solubility of NiNc in noncoordinating solvents prevented transient absorption data from being obtained for this compound. However, the TDDFT calculations were used to make speculations about the photoproperties.     

Solvation of carbohydrates in n,n'-dialkylimidazolium ionic liquids: a multinuclear NMR spectroscopy study

The solvation of carbohydrates in N, N'-dialkylimidazolium ionic liquids (ILs) was investigated by means of 13C and 35/37Cl NMR relaxation and 1H pulsed field gradient stimulated echo (PFG-STE) diffusion measurements. Solutions of model sugars in 1- n-butyl-3-methylimidazolium chloride ([C4mim]Cl), 1-allyl-3-methylimidazolium chloride ([CC2mim]Cl), and 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) were studied to evaluate the effects of cation and anion structure on the solvation mechanism. In all cases, the changes in the relaxation times of carbon nuclei of the IL cations as a function of carbohydrate concentration are small and consistent with the variation in solution viscosities. Conversely, the 35/37Cl and 13C relaxation rates of chloride ions and acetate ion carbons, respectively, have a strong dependency on sugar content. For [C2mim][OAc], the correlation times estimated from 13C relaxation data for both ions reveal that, as the carbohydrate concentration increases, the reorientation rate of the anion decreases faster than that of the cation. Although not as marked as the variations observed in the relaxation data, similar trends were obtained from the analysis of cation and, in the case of [C2mim][OAc], anion self-diffusion coefficients of the sugar/IL systems. Our results show that the interactions between the IL cation and the solutes are nonspecific, confirm that the process is governed by the interactions between the IL anion and the carbohydrate, and, more importantly, indicate no change in the solvation mechanism regardless of the structure of the anion.     

Prediction of heterofullerene stabilities: a combined DFT and chemometric study of C56Pt2, C57Pt2 and C81Pt2

A systematic search of the regioisomers of the heterofullerenes, C57Pt2 and C56Pt2, has been carried out by means of density functional calculations to find the most stable structures. Both heterofullerenes incorporate two metal atoms into the fullerene surface. In the case of C57Pt2, one platinum atom substitutes one carbon atom of C60 and the other platinum atom replaces a C--C bond, whereas in C56Pt2 each platinum atom replaces one C--C bond. Several geometric factors were studied, three of which have particularly important effects on the relative stabilities of the regioisomers: the Pt--Pt separation, the number of C--C bonds remaining after substitution, and the type of C--C bond that is substituted. All these factors indicate that the deformation of the carbon framework is a general factor that governs the relative stabilities of the regioisomers. Because a high number of factors affect the stability of the heterofullerenes we also used chemometric techniques in this study. Partial least-squares (PLS) regression was used to establish the structure-energy relationships of C57Pt2 and C56Pt2 heterofullerenes. The understanding gained of the factors that affect the relative isomers stabilities has allowed us to predict the stabilities of larger disubstituted carbon cages, for example, C81Pt2 heterofullerene.     

A DFT/TDDFT study of the structural and spectroscopic properties of Al(III) complexes with 4-nitrocatechol in acidic aqueous solution

The complexation of 4-nitrocatechol in aqueous solution at pH 5 has been studied by molecular spectroscopy combined with quantum chemical calculations. In these physico-chemical conditions, the formation of the two complexes [4ncatAl(H₂O)₄]⁺ and [(4ncat)₂Al(H₂O)₂]⁻ has been highlighted. The electronic absorption spectra of the 1:1 and 1:2 complexes of Al(III) with 4-nitrocatechol have been computed using the time-dependent density functional theory and the polarizable continuum model. It turns out that the 6-311+G(d,p) basis set provides a good agreement between experimental and theoretical absorption spectra. This good agreement has allowed the determination of the preferential conformation of the 1:2 complex in aqueous solution. A complete assignment of the UV–Vis absorption and Raman spectra of the complexes has been proposed.     

Conformational analysis of N-Boc-N,O-isopropylidene-α-serinals. A combined DFT and NMR study

This work describes an extensive conformational analysis of Garner's aldehyde and its α-methylated homologue—two important chiral building blocks that are widely used in organic synthesis. A combination of density-functional theory and NMR spectroscopy confirmed the existence of a dynamic equilibrium between two possible conformers of the carbamate group in these compounds. The calculated properties such as conformer populations and rotational barriers around the (CO)-N bond are in good agreement with the experimental values. Finally, the dipole moments of the molecules appear to be a decisive factor in the stabilization of the conformers in solution.     

Reconsideration on hydrogen bond strengthening or cleavage of photoexcited coumarin 102 in aqueous solvent: a DFT/TDDFT study

In this work, the excited-state hydrogen bonding dynamics of photoexcited coumarin 102 in aqueous solvent is reconsidered. The electronically excited states of the hydrogen bonded complexes formed by coumarin 102 (C102) chromophore and the hydrogen donating water solvent have been investigated using the time-dependent density functional theory method. Two intermolecular hydrogen bonds between C102 and water molecules are considered. The previous works (Wells et al., J Phys Chem A 2008, 112, 2511) have proposed that one intermolecular hydrogen bond would be strengthened and the other one would be cleaved upon photoexcitation to the electronically excited states. However, our theoretical calculations have demonstrated that both the two intermolecular hydrogen bonds between C102 solute and H(2)O solvent molecules are significantly strengthened in electronically excited states by comparison with those in ground state. Hence, we have confirmed again that intermolecular hydrogen bonds between C102 chromophore and aqueous solvents are strengthened not cleaved upon electronic excitation, which is in accordance with Zhao's works.     

Binuclear terephthalato-bridged copper(II) complex with N2O2 coordinating tripodal ligand: synthesis,structure, magnetic properties,and DFT study

The bluish green binuclear dicarboxylato bridged copper(II) complex [Cu₂(HL)₂(µ-tp)], 1 has been synthesized, where (HL^?) is the monodeprotonated form of N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine and tp = terephthalate dianion. Herein, we report the synthesis, spectral and structural characterization, and magnetic behavior of 1. The coordination geometry of Cu(II) has a distorted square pyramidal geometry (τ = 0.117). The variable temperature magnetic moment reveals that the complex exhibits very weak antiferromagnetic interaction (J _Exp = ?0.30 cm^?1) and the calculated J value (J _Calcd = ?1.05 cm^?1) using broken symmetry DFT method is in agreement with the experimentally observed value.     

Site selectivity in the protonation of a phosphinito bridged Pt(I)-Pt(I) complex: a combined NMR and density-functional theory mechanistic study

The protonation of the dinuclear phosphinito bridged complex [(PHCy2)Pt(mu-PCy2){kappa(2)P,O-mu-P(O)Cy2}Pt(PHCy2)] (Pt-Pt) (1) by Br?nsted acids affords hydrido bridged Pt-Pt species the structure of which depends on the nature and on the amount of the acid used. The addition of 1 equiv of HX (X = Cl, Br, I) gives products of formal protonation of the Pt-Pt bond of formula syn-[(PHCy2)(X)Pt(mu-PCy2)(mu-H)Pt(PHCy2){kappaP-P(O)Cy2}] (Pt-Pt) (5, X = Cl; 6, X = Br; 8, X = I), containing a Pt-X bond and a dangling kappa P-P(O)Cy2 ligand. Uptake of a second equivalent of HX results in the protonation of the P(O)Cy2 ligand with formation of the complexes [(PHCy2)(X)Pt(mu-PCy2)(mu-H)Pt(PHCy2){kappaP-P(OH)Cy2}]X (Pt-Pt) (3, X = Cl; 4, X = Br; 9, X = I). Each step of protonation is reversible, thus reactions of 3, 4, with NaOH give, first, the corresponding neutral complexes 5, 6, and then the parent compound 1. While the complexes 3 and 4 are indefinitely stable, the iodine analogue 9 transforms into anti-[(PHCy2)(I)Pt(mu-PCy2)(mu-H)Pt(PHCy2)(I)] (Pt-Pt) (7) deriving from substitution of an iodo group for the P(OH)Cy2 ligand. Complexes 3 and 4 are isomorphous crystallizing in the triclinic space group P1 and show an intramolecular hydrogen bond and an interaction between the halide counteranion and the POH hydrogen. The occurrence of such an interaction also in solution was ascertained for 3 by (35)Cl NMR. Multinuclear NMR spectroscopy (including (31)P-(1)H HOESY) and density-functional theory calculations indicate that the mechanism of the reaction starts with a prior protonation of the oxygen with formation of an intermediate (12) endowed with a six membered Pt(1)-X...H-O-P-Pt(2) ring that evolves into thermodynamically stable products featuring the hydride ligand bridging the Pt atoms. Energy profiles calculated for the various steps of the reaction between 1 and HCl showed very low barriers for the proton transfer and the subsequent rearrangement to 12, while a barrier of 29 kcal mol(-1) was found for the transformation of 12 into 5.     

Solvation and aggregation of n,n'-dialkylimidazolium ionic liquids: a multinuclear NMR spectroscopy and molecular dynamics simulation study

The solvation and aggregation of the ionic liquid (IL) 1-n-butyl-3-methylimidazolium chloride ([C4mim]Cl) in water and dimethylsulfoxide (DMSO) were examined by analysis of (1)H and (35/37)Cl chemical shift perturbations and molecular dynamics (MD) simulations. Evidence of aggregation of the IL n-butyl chains in aqueous environments at IL concentrations of 75-80 wt% was observed both in the NMR experiments and in the MD simulations. The studies also show that [C4mim]Cl behaves as a typical electrolyte in water, with both ions completely solvated at low concentrations. On the other hand, the data reveal that the interactions between the [C4mim](+) and Cl(-) ions strengthen as the DMSO content of the solutions increases, and IL-rich clusters persist in this solvent even at concentrations below 10 wt%. These results provide an experimentally supported atomistic explanation of the effects that these two solvents have on some of the macroscopic properties of [C4mim]Cl. The implications that these findings could have on the design of IL-based solvent systems are briefly discussed.     

Structural, theoretical and multinuclear NMR study of mercury(II) complexes with a new ambidentate phosphorus ylide

The reaction of the new ambidentate ylide, Ph₃PCHCOCH₂COOC₂H₅ (EAPPY), with HgX₂ (X = Cl, Br and I) in equimolar ratios using methanol as the solvent leads to binuclear complexes of the type [EAPPY·HgX₂]₂ (X = Cl (1), Br (2) and I (3)). Single crystal X-ray analysis reveals the presence of a centrosymmetric dimeric structure containing the ylide and HgX₂ (X = Br or I)_. The IR and NMR data of the product [(EAPPY)·HgCl₂]₂ (1), formed by the reaction of mercury(II) chloride with the same ylide, are similar to those of 2 and 3. Analytical data indicate a 1:1 stoichiometry between the ylide and Hg(II) halide in each of the three products. Theoretical studies indicate that the nature of the R group in ylides of the type Ph₃PCHCOR has a weak effect on the Hg-C(ylide) bond length in binuclear Hg₂L₂I₄ complexes.     

Complexation reactions,electronic properties,and reactivity descriptors of cysteamine-based ligands in aqueous solution: a PCM/DFT study

Computational approaches based on density functional theory (DFT) combined with polarizable continuum model (PCM) of solvation have been used to probe the likelihood of complexation in water between oxo-vanadium(IV) and various medicinal cysteamine-based ligands. The experimental electronic spectra of a complex formed by oxo-vanadium(IV) and penicillamine in water agree well with the theoretical spectra based on the time-dependent density functional theory (TD-DFT) calculations. Among all density functionals adopted, CAM-B3LYP outperforms the others in predicting both structural and spectroscopic properties of oxo-transition metal complexes of cysteamine-based ligands. A variety of chelation behaviors have been found for the ligands tested, depending on the choice of substituent added to the cysteamine backbone. Solvation has a great impact on the thermodynamic driving force for cysteine and its derivatives to undergo complexation. In all cases, the thiolate sulfur atom forms stronger coordination bond than either the amine nitrogen or carboxylate oxygen atoms. Based on the thermodynamic and nucleophilicity index calculations, penicillamine has the highest potential to form complex with oxo-vanadium(IV).     

The complexation of flurbiprofen with β-cyclodextrin: a NMR study in aqueous solution

The complexation process between racemic flurbiprofen and β-cyclodextrin in solution was investigated by 1D and 2D proton NMR spectroscopy. In the presence of β-cyclodextrin, the aromatic protons of flurbiprofen were the most affected, suggesting a strong involvement of the phenyl groups in the inclusion mechanism. The stoichiometry of the complex was determined by the method of continuous variation, using the chemical induced shifts of both host and guest protons. The association constant, K_a of the obtained complex was calculated and found to be 2483.8 M^?1. On the other hand, signals belonging to the protons associated with the carboxyl group are split in the presence of β-cyclodextrin indicating enantiomeric differentiation. Rotating frame NOE spectroscopy, (ROESY), was used to ascertain the solution geometry of the host–guest complex. The result suggested that the flurbiprofen molecule fully penetrates the β-cyclodextrin cavity with the carboxyl group protruding from the primary hydroxyl side and the phenyl group close to the secondary rim.     

Theoretical analysis of frontier orbitals,electronic transitions,and global reactivity descriptors of M(CO)4L2 type metal carbonyl complexes: a DFT/TDDFT study

Structural Chemistry - Metal carbonyl complexes, which have been known as effective catalysts since early days, find use in many fields both directly and indirectly. Although the use of metal...