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.

Polymer structures with tunable symmetry and sizes are desired for applications such as lithography, filtration membranes, and separation. Here we report the self-assembled supramolecular hexagonal columnar (ΦH) structures with tunable lattice size varying from 5 to 7 nm by constructing hydrogen-bonded copolymers bearing poly­(4-vinylpyridine) (P4VP) and two dendritic molecular additives, 1-[4′-(3″,4″,5″-tridecyloxybenzoyloxy)­phenyleneoxycarbonyl]-3-[(4″-hydroxyphenyl)­oxycarbonyl]­benzene (12CBP) and 4-hydroxyphenyl (3,4,5-tridecyloxy)­benzoate (12CTB). Despite the distinct molecular size difference between 12CBP and 12CTB, the resulting ternary supramolecular copolymers, P4VP­(12CBP) x (12CTB) y , possess a homogeneous ΦH phase at x ≥ 0.1 and y ≥ 0.2. Each column is constructed with P4VP as the backbone tethered with mixed side chains. The column diameter is between the size of the corresponding P4VP­(12CBP) x+y and P4VP­(12CTB) x+y and could be easily tuned by varying x and y. The enhancement of ΦH in supramolecular copolymers is attributed to the entropy effect of the mixed side chain and enthalpy effect from hydrogen bonding interaction of the P4VP backbone and two molecules (12CBP and 12CTB).