Magnetic Field-Induced Self-Assembly of Conjugated Block Copolymers and Nanoparticles at the Air-Water Interface.

Here, we report the magnetic field-induced self-assembly of a conjugated block copolymer, poly(3-hexylthiopene)-block-poly(ethylene glycol) (P3HT-b-PEG), and iron oxide nanoparticles (IONPs) at the air-water interface. Binary self-assembly of P3HT-b-PEG and IONPs at the interface results in nanoparticle-embedded P3HT-b-PEG nanowire arrays with a micrometer-scale domain size. Under the magnetic field, the field-induced magnetic interaction significantly improves the degree of order, generating long-range ordered, direction-controlled nanoarrays of P3HT-b-PEG and IONPs, where IONPs are aligned in the direction of the magnetic field over a sub-millimeter scale. The size of IONPs is an important factor for the formation of an ordered assembly structure at the nanometer scale, as it dictates the magnetic dipole interaction and the entropic interaction between nanoparticles and polymers. The consideration of magnetic dipole interactions suggests that the field-induced self-assembly occurs through the formation of intermediate magnetic subunits composed of short IONP strings along the semirigid P3HT nanowires, which can be aligned through the magnetic interactions, ultimately driving the long-range ordered self-assembly. This study demonstrates for the first time that the magnetic field-induced self-assembly can be used to generate macroscopically ordered polymer films with a nanometer-scale order in low fields.

Responsive Thin-Film Interference Colors from Polaronic Conjugated Block Copolymers.

Colors responsive to the chemical environment can form the basis for simple and highly accessible diagnostic tools. Herein, the charge modulation of conjugated polymers is demonstrated as a new mechanism for chemically responsive structural colors based on thin-film interference. A liquid-liquid interfacial self-assembly is employed to create a conjugated block copolymer film that is flexible, transferable, and highly homogeneous in thickness over a large area. Gold (Au) complexes are introduced in the self-assembly process for in situ oxidation of conjugated polymers into a hole-polaronic state that renders the polymer film responsive to the chemical environment. When transferred onto a reflective substrate, the film shows thickness-dependent tunable reflective colors due to the optical interference. Furthermore, it experiences drastic changes in its dielectric behavior upon switching of the polaronic state, thereby enabling large modulations to the interferometric colors. Such responsive thin-film colors, in turn, can be used as a simple and intuitive multicolor readout for the recognition of reductive vapors including biological decomposition products.