New Surfactant Phosphine Ligands and Platinum(II) Metallosurfactants. Influence of Metal Coordination on the Critical Micelle Concentration and Aggregation Properties

摘要

We have prepared the first platinum(II) metallosurfactants from a new family of linear surfactant phosphines Ph2P(CH2)nSO3Na {1 (n=2), 2 (n=6), and 3 (n=10)}, which were synthesized by reaction between the halosulfonates X(CH2)nSO3Na and sodium diphenylphosphide. The metallosurfactants cis-[PtCl2L2] (L = 1-3) were obtained after reaction between the phosphines and PtCl2 in dimethylsulfoxide. All compounds were fully characterized by the usual methods {NMR (1H, 13C, 31P, 195Pt), IR, MS-ESI and HRMS}. By exploring the surfactant properties of phosphines 1-3 and their respective platinum metallosurfactants cis-[PtCl2L2] (L = 1-3) through surface tension measurements, dynamic light scattering spectroscopy, and cryo-TEM microscopy, we were able to analyze the influence of the metal coordination on the critical micelle concentration (cmc) and the aggregation properties. The cmc values of platinum metallosurfactants were considerably lower than those obtained for the free phosphines 1-3. This behavior could be understood by an analogy between the structure of cis-[PtCl2L2] complexes and bolaform surfactants. The calculated values of area per molecule also showed different tendencies between 1-3 and cis-[PtCl2L2] complexes, which could be explained on the basis of the possible conformations of these compounds in the air-water interface. The study of aggregates by dynamic light scattering spectroscopy and cryo-TEM microscopy showed the formation of spherical disperse medium size vesicles in all cases. However, substantial differences were observed between the three free phosphines (the population of micellar aggregates increased with long chain length) and also between phosphines and their respective metallosurfactants.