Tunable Supramolecular Hexagonal Columnar Structures of Hydrogen-Bonded Copolymers Containing Two Different Sized Dendritic Side Chains

Abstract

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).

Supramolecular Fluorescent Polymers Containing α-Cyanostilbene-Based Stereoisomers: Z/E-Isomerization Induced Multiple Reversible Switching

“…In recent years, supramolecular side-chain polymers prepared via noncovalent interactions between polymers and molecular additives have been extensively used in construction and fabrication of various hierarchical nanostructures as well as directed assembly of functional molecules within polymer matrix. − The supramolecular approach offers a facile and efficient route for exploration of novel functional materials with tailored properties, together with solution processability and mechanical properties offered by the polymer chains. Motivated by these advantages, we propose to introduce α-cyanostilbene and its derivatives into supramolecular polymers.…”

Stronger Intermolecular Forces or Closer Molecular Spacing? Key Impact Factor Research of Gelator Self-Assembly Mechanism

“…Typically, three major scattering peaks (2θ = 3.6°, 6.1° and 7.2°; Figure a) get the d spacing of 24.5, 14.4, and 12.3 Å, respectively. They appear in a ratio of 1:1/√3:1/2 in the Glu-CBZ scattering pattern, and this ratio corresponds to a hexagonal columnar structure . In the meanwhile, the scattering peaks of Glu-DPA (2θ = 3.5°, 7.5°, 10.5°; Figure a) get the d spacing of 25.2, 11.8, and 8.4 Å (the ratio = 1:√2/3:1/3) and correspond to a columnar square structure .…”

Construction of Supramolecular Nanostructures from V-Shaped Amphiphilic Rod-Coil Molecules Incorporating Phenazine Units

“…This result further implies that lateral alkoxy groups at the dibenzo[ a , c ]phenazine rod building block significantly affect the phase transition temperatures of molecules. On slow cooling of 1 and 2 , from the isotropic liquid to crystalline mesophase, a focal conical fan texture with arced striations and a spherulitic fan texture are observed by POM experiment, respectively, which could preliminarily suggest the presence of hexagonal symmetry ( Figure 2 ) [ 40 , 41 , 42 , 43 ].…”