Entropically Driven Self‐Assembly of Bolaamphiphilic Perylene Dyes in Water

Abstract

AbstractThe specific hydrophobic effect involved in the self‐assembly of a bolaamphiphilic perylene bisimide (PBI) dye bearing oligoethylene glycol (OEG) chains has been identified. In pure water, the self‐assembly is entropically driven and enthalpically disfavored, as explored by optical spectroscopy and isothermal titration calorimetry studies. Besides strong π–π interactions between the PBI units that are primarily of enthalpic nature, the major contribution to the self‐assembly is the gain of entropy by release of confined water molecules from the hydration shell of the hydrophilic OEG moieties. Both contributions favor self‐assembly, but their countervailing thermodynamic parameters are reflected in an uncommon temperature dependence, which can be inverted upon gradual addition of an organic cosolvent that makes the π–π interaction increasingly dominant.