Solvent and Temperature Dependencies of the Rates of Thermal Cis-to-Trans Isomerization of Tetra-(ortho)substituted 4-Aminoazobenzenes Containing 2,6-Dimethoxy Groups.

The kinetics of thermal cis-to-trans isomerization of two tetra-(ortho)substituted 4-aminoazobenzene derivatives containing 2,6-dimethoxy groups in the 4-aminobenzene ring and either 2',6'-dimethyl (1) or 2',6'-dichloro groups in another ring was studied in 16 and 9 solvents, respectively, at room temperature. In addition, the kinetics of isomerization of 1 was studied at variable temperatures in 6 solvents. The solvent effects were analyzed in terms of multiparameter correlations using the Kamlet-Taft, Catalan, and Laurence scales. The temperature dependencies were analyzed in terms of the isokinetic relationship by using Exner's method. The correlation analysis was also extended to several previously reported systems, including isomerization of unsubstituted 4-aminoazobenzene and push-pull 4-NR2-4'-NO2 azobenzenes. It was established that for all 4-aminoazobenzenes in contrast to push-pull azobenzenes, the increase in solvent dipolarity does not affect or even inhibit isomerization rates; however, the increase in solvent acidity induces large rate accelerations. The isokinetic relationship holds only in aprotic solvents, while in alcohols and water, the temperature dependencies do not pass through the common point at T = Tiso, indicating different mechanisms operating in protic and aprotic solvents. The acceleration effect by protic solvents does not represent a type of general acid catalysis as follows from the small solvent isotope effect kH/kD = 1.26 in water. It is suggested that protic solvents induce a change in the reaction mechanism supposedly from inversion to rotation by hydrogen bonding stabilization of the negative charge developed on the azo group in a resonance structure involving a 4-amino group.

Zwitterion-neutral form equilibria and binding selectivity of pyridineboronic acids.

A 11B NMR study of 3-pyridineboronic acid at variable pH in water and 50 vol% aqueous dioxane confirms that the tautomeric equilibrium of the acid is shifted to the zwitterionic form in water, but to the molecular form in the mixed organic solvent. Interactions of 3- and 4-pyridineboronic acids with sialic acid, fructose and several other diols were studied by potentiometric titrations in a wide range of pH in water and water-organic mixtures. In all reaction media the stability of boronate complexes increases upon an increase in pH for neutral low acidic diols such as fructose and glucose but has the opposite trend for highly acidic sialic and lactic acids occurring as anionic species. The selectivity of pyridineboronic acids to sialate anions in an acidic medium is interpreted quantitatively by combining the pH-profiles with Brønsted type correlations for binding constants. In addition, mathematical expressions allowing one to predict the optimum pKa value of a boronic acid for the strongest binding of a given diol (sialic acid or fructose) at a given pH are suggested. The shifts in the tautomeric equilibrium induced by changing the solvent polarity in aqueous-organic mixtures are manifested in the magnitude of relative shifts of pKa of pyridineboronic acids induced by diol complexation.

Probing the Role of the Bridging Nitrogen in the Signaling Mechanism of an Anthracene-Boronic Acid Sugar Sensor and a Different Version of the PET-Based Mechanism.

The N-quaternized derivative 5 of the James-Shinkai anthracene-boronic acid fluorescence sugar sensor 1 was prepared to probe the role of the bridging nitrogen in the signaling mechanism of 1. Both 5 and 1 contain positively charged bridging groups NMe+ or NH+, respectively, but 5 lacks the ability to form the intramolecular ammonium-boronate doubly ionic hydrogen bond present in 1. Receptors 1 and 5 display opposite fluorescence vs pH profiles with a small turn-on effect of the sugar binding to the zwitterion of 5 in contrast to a large effect observed with 1. It is concluded that the ammonium-boronate hydrogen bond is essential for the signaling mechanism of 1. Its possible function is enabling the PET quenching effect by shifting the NH+ proton toward boronate anion inside the hydrogen bond, the degree of which is modulated by the ester formation with diols affecting the basicity of boronate anion. This mechanism agrees with observed signaling selectivity of 1 toward a series of di- and polyols of variable structures as well as with the behavior of 1 in buffered D2O and methanol solvents at controlled pH and provides an addition to the established "loose bolt" mechanism signaling mode essential for receptors with nonpolar fluorophores.

Anion Recognition by Benzoxaborole.

The binding types (H-bonding or coordinate) and stability constants for complexes of 11 mono- and di-anions with benzoxaborole (1) were determined by 1H and 11B NMR titrations in DMSO or MeCN. Compared to phenylboronic acid (PBA), 1 is a stronger Lewis acid and a poorer H-bond donor with only one B-OH group, which is expected therefore to recognize anions mostly through the coordinate bonding. This is the case however only with F-, HPO42-, and PhPO32- anions, which are coordinately bonded to 1, and partially with SO42-, which forms only the H-bonded complex with PBA, but both H-bonded and coordinate complexes with 1. The majority of tested anions (AcO-, PhPO3H-, (PhO)2PO2-, Cl-, and Br-) form H-bonded complexes with both 1 and PBA, whereas H2PO4- changes the binding mode from coordinate for PBA to H-bonded for 1. The preferable binding type for each anion is confirmed by calculations of DFT-optimized structures of the anion complexes of 1. The preferable binding type can be rationalized considering the effects of the steric hindrance, more significant for the coordinate bonding, and of increased anion basicity, which is favorable for both binding types, but enhances the strength of coordinate bonding more significantly than the strength of H-bonding.