ABSTRACT
Water in our environment is ever present, particularly in our atmosphere, from which it may be adsorbed by materials hygroscopically. At the molecular level, the binding of water molecules to various materials is driven by weak interactions but can have profound effects on physical properties, including the donor-acceptor interactions in charge transfer (CT) salts. Herein we present the unexpected three-state hydrochromatic switching of a bipyridinium-based donor-acceptor self-complex with changes in relative humidity (RH) and subsequent stable hydrate formation. RH is typically an overlooked variable that can vary greatly. These findings suggest that care should be taken to consider fluctuations in RH when characterizing the solid state optical band gap and CT absorption bands for organic donor-acceptor CT salt complexes.
ABSTRACT
The addition of molecular recognition units into structures of amphiphiles is a means by which soft matter capable of undergoing template-directed micellization can be obtained. These supramolecular amphiphiles can bind with molecular templates using non-covalent bonding interactions, forming host-guest complexes that hold the amphiphiles together as they undergo micellization. In most cases, such templates are synthesized and designed for a specific molecular recognition motif. It is not clear, however, to what extent these types of amphiphile systems are responsive to members of a biologically derived class of molecular targets, for example, melatonin receptor agonists and their numerous isosteres. Herein, we describe the template-directed micellization and arrangement at the air-water interface of a bipyridinium-based gemini surfactant, driven by the influence of donor-acceptor CT interactions with a series of bioactive classical and non-classical melatonin isosteres. Under the conditions of templation by either 5-methoxytryptophol, N-acetylserotonin, N-acetyltryptamine, or the pharmaceutical agent agomelatine, favorable Gibbs free energies of micellization were observed with decreases in CMC by up to 70%, and concomitant increases of 28% in surface pressure, and decreases of 20% in contact angle versus untemplated solutions. Solid state thermochromic transition temperatures for inkjet-printed patterns of the templated amphiphile solutions were inversely correlated with trends observed for their respective CMCs, and exhibited no correlation to their binding constants. These findings contend for the generalizable use of melatonin receptor agonists as targets and/or templates for chemical systems, which rely on π-stacking donor-acceptor CT interactions in water to facilitate the actions of binding, sequestration, or template-directed self-assembly.