NMR and theoretical study of the cooperative interaction of hydrated proton with dibenzo-24-crown-8

Interaction of hydrated protons (HPs) with dibenzo-24-crown-8 (DBC in nitrobenzene-d(5) was studied by (1)H and (13)C NMR under assistance of ab initio-density functional theory (DFT) quantum calculations. HPs were afforded by hydrogen bis(1,2-dicarbollyl) cobaltate (HDCC) with 3.5 M excess of H(2)O. The forming of a complex between HP and DBC leads to marked and additive relative shifts of both (1)H and (13)C signals. This was utilized for the estimation of the stabilization constant K of the complex. Its value is at least 10(6) l/mol, which agrees with the result of independent extraction method (log K = 6.3). Using absolute integral intensities of the HP signal in a water-saturated system, it was shown that the form of HP present in the complex must be H(5)O(2)(+), in accord with formerly published structure of the complex in crystalline form. The investigation of the dynamics of exchange between bound and free DBC by transverse relaxation using variably spaced pulses in the Carr-Purcell-Meiboom-Gill (CPMG) sequence or on-resonance rotating-frame relaxation with variable spin-lock field intensity was partly hampered by the fast relaxation of some signals in the complex because of relative immobilization of its internal motions. In order to remove these effects, a pulse sequence dipolar interaction-free transverse relaxation (DIFTRE) for static DIFTRE was devised and the MLEV17 pulse sequence with high intensity of electromagnetic field was used in a separate series of experiments. Using the results of these latter experiments, the correlation time of exchange was established to be about 0.8 ms, which complied with the shape of the spectra. The accompanying ab initio DFT calculations showed that the apparent symmetry of the molecules of both DBC and its complex with H(5)O(2)(+) was probably the result of averaging of energetically close conformations (five for DBC and four for the complex). Both NMR and the calculations show that the basic mode of binding of the ion in the complex is analogous to that found in crystal but the most pronounced conformation is slightly different.