Hydrogen-bonded mesomorphic complexes combining hydrophilic and fluorophilic molecular segments.

A 2,4-diamino-6-phenyl-1,3,5-triazine carrying a single oligo(ethylene oxide) (EO) chain has been investigated in binary mixtures with two-chain and three-chain semiperfluorinated benzoic acids. Mixtures of the triazine with three equivalents of the complementary acids exhibit a hexagonal columnar (Col) mesophase. Docking of three acid molecules to the diaminotriazine nucleus leads to the formation of disc-like aggregates with a central hydrogen-bonded polar core surrounded by the peripheral fluoroalkyl chains, which self-assemble in columns arranged on a hexagonal lattice.

Polyphilic hydrogen bonded block molecules involving semiperfluorinated and silylated molecular fragments.

2,4-Diamino-6-phenyl-1,3,5-triazines grafted with one or two semiperfluorinated chains at the phenyl substituent have been investigated in binary mixtures with one-chain and two-chain oligo(dimethylsiloxy) terminated 4-alkoxy- and 3,4-dialkoxybenzoic acids. Equimolar mixtures of the triazines with the complementary acids form discrete double hydrogen-bonded heterodimers with an elongated central core. Mesomorphic properties are observed only if at least two terminal fluoroalkyl chains are attached to the triazine entity.

Chirality Synchronization of Hydrogen-Bonded Complexes of Achiral N-Heterocycles.

2,4-Diamino-6-phenyl-1,3,5-triazines carrying a single oligo(ethylene oxide) (EO) chain form an optically isotropic mesophase composed of a conglomerate of macroscopic chiral domains with opposite sense of chirality even though the constituent molecules are achiral. This mesophase was proposed to result from the helical packing of hydrogen-bonded triazine aggregates, providing long-range chirality synchronization. The results provide first evidence for macroscopic achiral symmetry breaking upon conglomerate formation in an amorphous isotropic phase formed by hydrogen-bonded associates of simple N-heterocycles that are related to prebiotic molecules.

Mesomorphic hydrogen-bonded complexes of complementary semiperfluorinated components.

2,4-Diamino-6-phenyl-1,3,5-triazines carrying one or two semiperfluorinated chains at the phenyl substituent have been investigated in binary mixtures with partially fluorinated benzoic acids by polarizing microscopy, differential scanning calorimetry, and X-ray diffraction. The number and positions of the fluorinated tails of the acid component were systematically modified. Equimolar mixtures of the triazines with the aromatic acids form discrete hydrogen-bonded heterodimers with an elongated central core.