Aromatic and Aliphatic CH Hydrogen Bonds Fight for Chloride while Competing Alongside Ion Pairing within Triazolophanes

Triazolophanes are used as the venue to compete an aliphatic propylene CH hydrogen-bond donor against an aromatic phenylene one. Longer aliphatic C-H center dot center dot center dot Cl- hydrogen bonds were calculated from the location of the chloride within the propylene-based triazolophane. The gasphase energetics of chloride binding (Delta G(bind), Delta H-bind, Delta S-bind) and the configurational entropy (Delta S-config) were computed by taking all low-energy conformations into account. Comparison between the phenylene- and propylene-based triazolophanes shows the computed gas-phase free energy of binding decreased from Delta G(bind) = -194 to -182 kJ mol(-1), respectively, with a modest enthalpy entropy compensation. These differences were investigated experimentally. An H-1 NMR spectroscopy study on the structure of the propylene triazolophane's 1:1 chloride complex is consistent with a weaker propylene CH hydrogen bond. To quantify the affinity differences between the two triazolophanes in dichloromethane, it was critical to obtain an accurate binding model. Four equilibria were identified. In addition to 1:1 complexation and 2:1 sandwich formation, ion pairing of the tetrabutylammonium chloride salt (TBA(+)center dot Cl-) and cation pairing of TBA(+) with the 1:1 triazolophane chloride complex were observed and quantified. Each complex was independently verified by ESI-MS or diffusion NMR spectroscopy. With ion pairing deconvoluted from the chloride receptor binding, equilibrium constants were determined by using H-1 NMR (500 mu M) and UV/Vis (50 mu M) spectroscopy titrations. The stabilities of the 1:1 complexes for the phenylene and propylene triazolophanes did not differ within experimental error, Delta G=(-38+2) and (-39 +/- 1) kJ mol(-1), respectively, as verified by an NMR spectroscopy competition experiment. Thus, the aliphatic CH donor only revealed its weaker character when competing with aromatic CH donors within the propylene-based triazolophane.