Photoresponsive materials play an important role in smart sensors and readable optical devices. The α-cyanostilbene moiety gathers Z/E-isomerization, mesogenic, and aggregation-induced enhanced emission (AIEE) properties together and can be considered as a multifunctional building block bearing luminogen, AIEgen, mesogen, and chromphore characteristics. Here, we report isomerization induced a series of notable reversible switching based on α-cyanostilbene containing hydrogen-bonded supramolecular polymers. Z- and E-stereoisomers of dendritic α-cyanostilbene derivatives (Z-CNBP and E-CNBP) were hydrogen-bonded with poly­(4-vinylpyridine) (P4VP), giving rise to P4VP­(Z-CNBP) x and P4VP­(E-CNBP) x . P4VP­(Z-CNBP) x exhibit a hexagonal columnar (Φh) phase at 0.4 ≤ x ≤ 1.0, while the lamellar phase could be formed for P4VP­(E-CNBP) x at 0.3 ≤ x ≤ 0.7. P4VP­(Z-CNBP)0.8 shows photothermal E/Z-isomerization induced reversible switching, including phase structures, surface topographies, birefringence, and fluorescence properties, whereas P4VP­(E-CNBP)0.5 exhibits enhanced fluorescence emission upon UV irradiation.

Polynorbornenes containing mesogenic side groups with a controlled number and substituted position were synthesized and their mesomorphic properties were systematically investigated.

The substituent position and number have an important effect on the supramolecular liquid crystalline structure evolution in side-chain polymers.