RESUMEN
The competition between host-guest binding and solvent interactions is a crucial factor in determining the binding affinities and selectivity of molecular receptor species. The interplay between these competing interactions, however, have been difficult to disentangle. In particular, the development of molecular-level descriptions of solute-solvent interactions remains a grand experimental challenge. Herein, we investigate the prototypical halide receptor meso-octamethylcalix[4]pyrrole (OMCP) complexed with either chloride or bromide anions in both dichloromethane (DCM) and chloroform (trichloromethane, TCM) solvent using ultrafast infrared transient absorption and 2D IR spectroscopies. OMCP·Br- complexes in both solvents display slower vibrational relaxation dynamics of the OMCP pyrrole NH stretches, consistent with weaker H-bonding interactions with OMCP compared to chloride and less efficient intermolecular relaxation to the solvent. Further, OMCP·Br- complexes show nearly static spectral diffusion dynamics compared to OMCP·Cl-, indicating larger structural fluctuations occur within chloride complexes. Importantly, distinct differences in the vibrational spectra and dynamics are observed between DCM and TCM solutions. The data are consistent with stronger and more perturbative solvent effects in TCM compared to DCM, despite DCM's larger dielectric constant and smaller reported OMCP·X- binding affinities. These differences are attributed to the presence of weak H-bond interactions between halides and TCM, in addition to competing interactions from the bulky tetrabutylammonium countercation. The data provide important experimental benchmarks for quantifying the role of solvent and countercation interactions in anion host-guest complexes.