Entropically and enthalpically driven self-assembly of a naphthalimide-based luminescent organic π-amphiphile in water.

The self-assembly of π conjugated systems in water has emerged as an efficient method for the development of functional materials for biological applications. But the process is more difficult to understand and to control in water compared to organic solvents due to hydrophobic effects. For π-conjugated molecules, self-assembly in solution generally occurs due to either an enthalpic or entropic gain, but designing π systems that undergo self-assembly both an entropically and enthalpically favorable process is challenging.

Solvent Geometry Regulated J- and H-Type Aggregates of Photoswitchable Organogelator: Phase-Selective Thixotropic Gelation and Oil Spill Recovery.

We demonstrate supramolecular polymerization and formation of 1D nanofiber of azobenzene based organogelator (AZO-4) in cyclic hydrocarbon solvents (toluene and methylcyclohexane). The AZO-4 exhibits J- and H-type aggregates in toluene: MCH (9 : 1) and MCH: toluene (9 : 1) respectively. The type of aggregate was governed by the geometry of the solvents used in the self-assembly process.

Entropy-Enthalpy Compensation in Solvent Geometry Regulated Supramolecular Polymerization of Luminescent Napthalimide via a Non-Cooperative, Isodesmic Mechanism.

Supramolecular polymers of π-conjugated systems are an important class of materials with fascinating functions and properties originated from the dynamic behavior and highly ordered molecular organizations. Here, a donor-π-acceptor based functionalized luminescent napthalene monoimide (NMI) undergoes J-type self-assembly by non-covalent interactions via a non-cooperative, isodesmic mechanism to form supramolecular 1D nanowire. The fundamental insights into the thermodynamics regulating the supramolecular polymerization were derived through the fitting of the isodesmic model to variable temperature UV/Vis data in linear (dodecane) and nonliner hydrocarbon (decalin) based solvents.

Anion-assisted supramolecular polymerization of luminescent organic π-conjugated chromophores in a moderately polar solvent: tunable nanostructures and their corresponding effects on electronic properties.

Supramolecular polymers of π-conjugated organic chromophores have emerged as promising candidates in organic electronics because of their dynamic and highly ordered molecular organization. Herein, we demonstrate the formation of luminescent, highly conducting supramolecular polymers of a functionalized naphthalimide π-chromophore-based organic semiconductor in a moderately polar organic solvent (tetrahydrofuran) by overcoming solute-solvent H-bonding assistance from fluoride anions. The polymerization is exclusively guided by the synergistic effects of cascade H-bonding (F⋯H-N- of primary amines, followed by -CO⋯H-N- of amides), π-π stacking and hydrophobic interactions.