Size does matter: how to control organization of organic dyes in aqueous environment using specific ion effects.

Understanding the role played by external factors on the organization of molecules has the potential to contribute greatly to fundamental research and applications in fields as diverse as nanotechnology, medicine, material chemistry, etc. Countless studies involve the organization of small organic molecules in environments rich in ionic species, yet their participation in molecular organization is often overlooked. Herein, we critically assess the organization in aqueous solution of the cationic cyanine dye, thiazole orange, in the presence of different monovalent sodium salts. Our findings clearly indicate that not all ions are identical with regards to the organization of thiazole orange molecules and specific ions effects are at play. The conventional Debye and Hückel model is not sufficient to explain our results, and the participation of ionic species in molecular organization is explained in terms of the recent theory of water matching affinity. Herein, by choosing the right counterion with the appropriate size, we have shown that it is possible to either induce a simple shift in the monomer-dimer equilibrium of thiazole orange or to turn on the formation of larger organized structures.