A surprising terminal-group effect on the structural and physical properties of an amorphous polymer is reported. We recently demonstrated that triptycene derivatives with substituents at the 1,8,13-positions show specific self-assembly behavior, enabling the formation of a well-defined “2D + 1D” structure based on nested hexagonal packing of the triptycenes. Upon terminal functionalization with a 1,8-substituted triptycene (1,8-Trip), a liquid polymer, polydimethylsiloxane (PDMS, M n = 18–24 kDa), turned into a highly viscous solid that exhibits birefringence at 25 °C. Small-angle and wide-angle X-ray scattering measurements revealed that the resulting telechelic PDMS assembles into a 2D + 1D structure, where layers of PDMS domains, formed between 2D assemblies of the triptycene termini, stack into a 1D multilayer structure with a layer spacing of 18–20 nm. Because of this structuring, the complex viscosity of the telechelic PDMS was dramatically enhanced, providing a value 4 orders of magnitude greater than that of the original PDMS. Remarkably, the structural and physical properties of PDMS were hardly changed upon terminal functionalization with another regioisomer of triptycene (1,4-Trip), which differs only in the substitution pattern.

Although a large number of polymers that contain triptycene units in the main chains have been developed, no polymer design using 1,8-substituted triptycene has been reported to date. In this study, we investigated the properties of linear homo- and copolymers obtained by ring-opening polymerization of a triptycene monomer bearing a macrocyclic olefin linked at its 1,8-position and its copolymerization with cyclooctene, respectively. We found that the introduction of triptycene with this substitution pattern leads to nanoscale molecular ordering, thereby greatly improving the physical properties of the polymers. The key to this remarkable behavior of 1,8-substituted triptycene-containing polymers is the formation of a particular two-dimensional assembly of the triptycene units by nested hexagonal packing, which aligns one-dimensionally while folding the polymer chains into a well-defined layered structure. The polymer design using 1,8-substituted triptycene can be applied to other polymers, unless their main chain contains functional groups capable of a strong intermolecular interaction such as hydrogen bonding.