Triblock Polyphiles through Click Chemistry: Self‐Assembled Thermotropic Cubic Phases Formed by Micellar and Monolayer Vesicular Aggregates

Three series of triblock polyphiles consisting of a rigid 4‐phenyl‐1,2,3‐triazole or 1,4‐diphenyl‐1,2,3‐triazole core with three lipophilic and flexible alkoxyl chains at one end and a polar glycerol group at the opposite end were synthesized by copper‐catalyzed azide–alkyne click reactions. Their mesophase behavior was studied by polarizing optical microscopy, differential scanning calorimetry, and XRD. Depending on alkyl chain length and core length, a transition from hexagonal columnar to ${{\it Pm}\bar 3n}$ ‐type cubic phases was observed. In the cubic phases, the molecules are organized as spherical objects. Remarkably, compounds with a longer core unit have a higher tendency to form these cubic phases, and their stability is strongly enhanced over those of the compounds with a shorter core, despite longer cores having a smaller cone angle and therefore being expected to disfavor the formation of spherical objects. There is a large difference in the number of molecules involved in the spherical aggregates formed by compounds with long and short cores. Whereas the aggregates in the cubic phases of the compounds with short rod units are small and could be regarded as micellar, the long‐core compounds form much larger aggregates which are regarded as a kind of monolayer vesicular aggregate.