Search

The synthesis, structural characterization, and binding properties of two unprecedented multitopic receptors for ion-pair recognition are described. We isolated two of the six possible diastereomeric deep cavitand receptors resulting from the installation of four phosphonate groups at the upper rim of a calix[4]pyrrole--resorcin[4]arene hybrid scaffold. The isolated tetra-phosphonate receptors display either three (iooo) or four (oooo) of their P=O groups oriented away from the deep and functionalized aromatic cavity. In contrast to analogous tetra-phosphonate resorcin[4]arene cavitands, the 14-membered macrocyclic rings that contain the P=O groups in the tetra-phosphonate calix[4]pyrrole cavitands are conformationally flexible, always adopting a conformation locating the phenyl substituents in equatorial position. The tetra-phosphonate calix[4]pyrroles exhibited larger affinity constants than the previously reported bis-phosphonate calix[4]pyrrole counterparts in the complexation of both tetramethylphosphonium and octylammonium chloride salts in nonpolar solvents. We demonstrated that the iooo diastereoisomer was able to function as a multitopic receptor for organic chloride salts by switching the geometry of the 1:1 ion-paired complex from receptor-separated to close-contact depending on the quaternary or primary nature of the cobound organic cation. The ion-paired 1:1 complexes formed between the diastereomeric receptors and organic chloride salts were studied and thermodynamically characterized in solution. The determined stability constant values were compared to those obtained for the bis-phosphonate counterparts. The structure of the TMPCl⊂7iooo complex was determined by X-ray structure, and its formation was also evidenced in the gas phase. [ABSTRACT FROM AUTHOR]

We describe the design, synthesis and conformational assignment of three diasteromeric bis-phosphonate cavitands based on an aryl extended calix[4]pyrrole tetrol scaffold. The diaster-eoisomers differ in the relative spatial orientation of the P=O groups installed at their upper rims. We demonstrate that these compounds act as heteroditopic receptors for ion pairs forming ion-paired 1:1 complexes with alkylammonium (quaternary and primary) chloride salts in dichloromethane (DCM) solution and in the solid-state. ¹H NMR titrations indicate that the complexes are highly stable thermodynamically and kinetically. In the case of tetraalkyl-phosphonium/ammonium chloride guests, the host featuring the two P=O groups directed outwardly with respect to the aromatic cavity, 4oo, produces the most thermodynamically stable complexes. Conversely, for the primary alkyl ammonium chloride, the most effective receptor is the diastereoisomer 4ii with the two P=O groups converging on top of the aromatic cavity. In the nonpolar DCM solvent, the size of the quaternary cation has a strong impact in the thermodynamic stability of the complexes and their binding geometry. We use 2D-ROESY experiments to map out the binding geometries of the 1:1 complexes formed in solution. The 1:1 complexes of the 4oo host with the chloride salts have a separated arrangement of the bouzid ion- pair. In contrast, those of the 4ii host display a close-contact arrangement. We also investigate the same complexation processes in acetonitrile (ACN) solution. Both the salt and the initially formed anionic complex are fully dissociated in this more polar solvent. The receptors show an analogous trend in their binding affinities for quaternary phosphonium/ammonium chlorLle salts to the one seen in DCM solution. However, in ACN solution, the magnitudes of the binding affinities are reduced significantly and the size of the cation does not play a role. In addition, the inversion in the trend of relative binding affinities of the complexes, which was revealed in DCM solution, is eradicated in ACN when changing the cation substitution from quatemary to primary. [ABSTRACT FROM AUTHOR]

Despite its ubiquity during the binding and sensing of fluoride, the role of bifluoride (HF2-) and its binding properties are almost always overlooked. Here, we give one of the first examinations of bifluoride recognition in which we use computer-aided design to modify the cavity shape of triazolophanes to better match with HF2-. Computational investigation indicates that HF2- and Cl- should have similar binding affinities to the parent triazolophane in the gas phase. Evaluation of the binding geometries revealed a preference for binding of the linear HF2- along the north–south axis with a smaller Boltzmann weighted population aligned east-west and all states being accessed rapidly through in-plane precessional rotations of the anion. While the ¹H NMR spectroscopy studies are consistent with the calculated structural aspects, binding affinities in solution were determined to be significantly smaller for the bifluoride than the chloride. Computed geometries suggested that a 20° tilting of the bifluoride (stemming from the cavity size) could account for the 25-fold difference between the two binding affinities, HF2- < Cl-. Structural variations to the triazolophane's geometry and electronic modifications to the network of hydrogen bond donors were subsequently screened in a stepwise manner using density functional theory calculations to yield a final design that eliminates the tilting. Correspondingly, the bifluoride's binding affinity (K ∼ 106 M-1) increased and was also found to remain equal to chloride in the gas and solution phases. The new oblate cavity appeared to hold the HF2- in a single east–west arrangement. Our findings demonstrate the promising ability of computer-aided design to fine-tune the structural and electronic match in anion receptors as a means to control the arrangement and binding strength of a desired guest. [ABSTRACT FROM AUTHOR]