Influence of the Attachment of a Gold(I) Phosphine Moiety at the Upper Rim of a Calix[4]pyrrole on the Binding of Tetraalkylammonium Chloride Salts

We report the synthesis of an unprecedented mono-gold(I) phosphine complex based on a “two wall” aryl-ethynyl extended calix[4]pyrrole. We describe and compare the binding properties of the parent 10α,20α-bis-aryl-ethynyl calix[4]pyrrole ligand and the prepared organometallic compound as receptors for tetraalkylammonium chloride salts in dichloromethane and acetone solutions. We describe the results of ¹H NMR, UV-vis titrations and isothermal titration calorimetry (ITC) experiments in DCM and acetone solution, aiming to thermodynamically characterize the formed complexes. The obtained results indicate a noticeable decrease in the binding affinity of the chloride for the mono-gold(I) receptor 1 compared to the parent ligand 2. The increase in the negative value of the electrostatic surface potential at the center of the aromatic ring of the gold(I) meso-aryl-ethynyl substituent serves to explain the observed results and the presence in solution of the chloride complex of 1 as a mixture of two conformers.