Felipe J. González

The association of neutral systems linked by hydrogen bond interactions: a quantitative electrochemical approach

The electrochemical characterization of the neutral–neutral association by hydrogen bonds was performed on the basis of voltammetric current measurements. The diffusion coefficient of the electroactive compound is modified by effect of association, this provoke important variations in the voltammetric current peak. As an example of the weak hydrogen bond between neutral complexes, it was determined that 1,4-benzoquinone (Q) and benzoic acid (HBz) can associate with a 1:1 stoichiometry with a conditional association constant between 10 and 15 M � 1 . The Q(HBz) complex geometry was optimized using density functional theory and Moller–Plesset perturbation theory. In both theories, the most stable geometry is flat and exhibits two hydrogen bond interactions: O–H ��� O and C–H ��� O interactions. The binding energy at our best level of theory was )7.7 kcal/mol, that supports the stability of the 1:1 Q–HBz complex and which is accord with the values of the conditional association constant obtained from the electrochemical method here described. 2002 Elsevier Science B.V. All rights reserved.

The electrochemical reduction of perezone in the presence of benzoic acid in acetonitrile

Abstract An electrochemical study using transient techniques of a quinone-type natural product, perezone, has been performed in acetonitrile and in the presence of benzoic acid. Using linear sweep voltametry and single potential step chronoamperometry, it was possible to establish that the reduction mechanism of perezone involves a monoelectronic charge-transfer step, followed by a protonation step and homogeneous charge transfer due to disproportionation of the protonated intermediate. The mechanism for the homogeneous charge-transfer step was found to be of the type DISP1 (disproportionation order one) from the results of double potential step chronoamperometry experiments. The occurrence of the DISP1 mechanism was provoked by the mildly acidic medium used in this study.

Nature of Electrogenerated Intermediates in Nitro-Substituted Nor-β- lapachones: The Structure of Radical Species during Successive Electron Transfer in Multiredox Centers

Electrochemical, spectroelectrochemical, and theoretical studies of the reduction reactions in nor-β-lapachone derivatives including a nitro redox center showed that reduction of the compounds involves the formation of several radical intermediates, including a biradical dianion resultant from the separate reduction of the quinone and nitro groups in the molecules. Theoretical descriptions of the corresponding Fukui functions f(αα)⁺ and f(ββ)⁺(r) and LUMO densities considering finite differences and frozen core approximations for describing the changes in electron and spin densities of the system allowed us to confirm these results. A description of the potential relationship with the obtained results and biological activity selectivity indexes suggests that both the formation of stable biradical dianion species and the stability of the semiquinone intermediates during further reduction are determining factors in the description of their biological activity.

Tacticity influence on the electrochemical reactivity of group transfer polymerization-synthesized PTMA.

Spectroscopic, thermal, and electrochemical characterization results are presented for the redox active polymer poly(2,2,6,6-tetramethyl-1-piperinidyloxy-4-yl methacrylate) or PTMA, synthesized by group transfer polymerization (GTP), and its precursors 4-hydroxy-tetramethylpiperidine-N-oxyl (HO-TEMPO) and 4-methacryloyloxy-tetramethylpiperidine-N-oxyl (MO-TEMPO). DSC analysis of synthesized PTMA showed that the glass transition temperature (T(g)) of the polymer structure occurs at 155 °C, corroborated by dynamic mechanical analysis (DMA), which is higher when compared with T(g) data for PTMA synthesized by other methods. Also, the amount of radical species present in PTMA synthesized by GTP reactions (100%) is higher than the values typically upon synthesizing PTMA by radical polymerization. Electrochemical and spectroelectrochemical-electron spin resonance studies in acetonitrile revealed two redox events in the PTMA polymer, one of which is reversible, accounting for ca. 80% of the spins in the polymer and giving rise to the battery behavior. The other redox event is irreversible, accounting for the remaining ca. 20% of spins, which has not previously been reported. These two redox events are linked to a structural property associated with the tacticity of the polymer, where the reversible feature (responsible for cathode behavior) is the dominant species. This corresponds to a number of isotactic domains of the polymer (determined by high temperature (1)H NMR). The second feature accounts for the three-line impurity observed in the ESR, which has been reported previously but poorly explained, associated to the number of heterotactic/syndiotactic triads.

Reduction of 2,3,5-triphenyl-2H-tetrazolium chloride in the presence of polyelectrolytes containing 4-styrenesulfonate moieties.

The redox behavior of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) in the presence of different polyelectrolytes such as poly(sodium 4-styrenesulfonate) (PSS), poly(sodium 4-styrenesulfonate-co-sodium maleate) at two different comonomer compositions (P(SS(1)-co-MA(1)) and P(SS(3)-co-MA(1))), poly(sodium acrylate-co-sodium maleate) (P(AA(1)-co-MA(1))), and poly(sodium acrylate) (PAA) is studied. Due to aromatic-aromatic interactions, the polyelectrolytes containing benzene sulfonate groups produce a decrease on the reduction rate of TTC in the presence of ascorbic acid (ASC) and a shift of the anodic and cathodic peaks to higher negative potentials for the electrochemical reaction of TTC. As an important conclusion, these effects are a function of the linear aromatic density of the polyelectrolytes.

Stacking of 2,3,5-triphenyl-2H-tetrazolium chloride onto polyelectrolytes containing 4-styrenesulfonate groups

Possible structural aspects are discussed that justify the different resistance to reduction of 2,3,5-triphenyl-2 H-tetrazolium chloride (TTC) both chemically (by reaction with ascorbic acid (ASC)) and electrochemically, in the presence of different polyelectrolytes such as poly(sodium 4-styrenesulfonate) (PSS), poly(sodium 4-styrenesulfonate- co-sodium maleate) at two different comonomer compositions (P(SS 1- co-MA 1) and P(SS 3- co-MA 1)), and poly(sodium acrylate- co-sodium maleate) (P(AA 1- co-MA 1)). Different dissociation constants are found for the complexes between TTC and the different polyelectrolytes by diafiltration (DF). Related to this, spectroscopical differences are also found by (1)H NMR and UV-vis spectroscopies. Dynamic light scattering (DLS) showed a higher tendency to undergo intermolecular aggregation for P(SS 1- co-MA 1) in the presence of TTC, a result that could be related with a higher tendency for TTC to form hydrophobic ion pairs as a consequence of single stacking with the benzene sulfonate groups (BS) of this polyelectrolyte. On the other hand, the lower tendency for PSS to undergo intermolecular aggregation could be attributable to a higher probability to form more hydrophilic adducts by means of double stacking with TTC.

Competition between Hydrogen Bonding and Proton Transfer during Specific Anion Recognition by Dihomooxacalix[4]arene Bidentate Ureas

Competition between hydrogen bonding and proton transfer reactions was studied for systems composed of electrogenerated dianionic species from dinitrobenzene isomers and substituted dihomooxacalix[4]arene bidentate urea derivatives. To analyze this competition, a second-order ErCrCi mechanism was considered where the binding process is succeeded by proton transfer and the voltammetric responses depend on two dimensionless parameters: the first related to hydrogen bonding reactions, and the second one to proton transfer processes. Experimental results indicated that, upon an increase in the concentration of phenyl-substituted dihomooxacalix[4]arene bidentate urea, voltammetric responses evolve from diffusion-controlled waves (where the binding process is at chemical equilibrium) into irreversible kinetic responses associated with proton transfer. In particular, the 1,3-dinitrobenzene isomer showed a higher proton transfer rate constant (∼25 M(-1) s(-1)) compared to that of the 1,2-dinitrobenzene (∼5 M(-1) s(-1)), whereas the 1,4-dinitrobenzene did not show any proton transfer effect in the experimental conditions employed.

Correlation between Hydrogen Bonding Association Constants in Solution with Quantum Chemistry Indexes: The Case of Successive Association between Reduced Species of Quinones and Methanol

The functional M05-2X together with the SMD solvent model have been used to calculate hydrogen bonding association constants in dimethylsulfoxide (DMSO) solution. Data of equilibrium constants in DMSO for the case of electrochemically generated dianions interacting with methanol have been considered to test the reliability of the chemistry theoretical approach. From this approach, it was found that the successive association constants involved in the formation of the complexes depend on a linear combination of three quantum chemistry indexes which are the ionization energy, the electron affinity, and the charge on the oxygen atom receiving the methanol molecule. Under this perspective, the stoichiometry of all the dianion-methanol complexes was explained on the basis of the relative strength of the hydrogen bonding interaction compared to that of the methanol-DMSO and methanol dimer complexes. This linear combination seems to be valid regardless of the nature of the dianion structure and the number of methanol molecules in the complex, which is a relevant finding to generalize the applicability of both the functional M05-2X and the SMD solvent model, to calculate association constants for any other neutral or anionic molecules interacting by hydrogen bonding with proton donors.