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Abstract Piezo‐ and pyroelectric materials are of interest, for example, for energy harvesting applications, for the development of tactile sensors, as well as neuromorphic computing. This study reports the observation of pyro‐ and piezoelectricity in thin surface‐attached polymer brushes containing zwitterionic and electrolytic side groups that are prepared via surface‐initiated polymerization. The pyro‐ and piezoelectric properties of the surface‐grafted polyelectrolyte brushes are found to sensitively depend on and can be tuned by variation of the counterion. The observed piezo‐ and pyroelectric properties reflect the structural complexity of polymer brushes, and are attributed to a complex interplay of the non‐uniform segment density within these films, together with a non‐uniform distribution of counterions and specific ion effects. The fabrication of thin pyroelectric films by surface‐initiated polymerization is an important addition to the existing strategies toward such materials. Surface‐initiated polymerization, in particular, allows for facile grafting of polar thin polymer films from a wide range of substrates via a straightforward two‐step protocol that obviates the need for multistep laborious synthetic procedures or thin film deposition protocols. The ability to produce polymer brushes with piezo‐ and pyroelectric properties opens up new avenues of application of these materials, for example, in energy harvesting or biosensing. 

Conjugated copolymers containing electron donor and acceptor units in their main chain have emerged as promising materials for organic electronic devices due to their tunable optoelectronic properties. Herein, we describe the use of direct arylation polymerization to create a series of fully π-conjugated copolymers containing the highly tailorable purine scaffold as a key design element. To create efficient coupling sites, dihalopurines are flanked by alkylthiophenes to create a monomer that is readily copolymerized with a variety of conjugated comonomers, ranging from electron-donating 3,4-dihydro-2 H -thieno[3,4- b ][1,4]dioxepine to electron-accepting 4,7-bis(5-bromo-3-hexylthiophen-2-yl)benzo[ c ][1,2,5]thiadiazole. The comonomer choice and electronic nature of the purine scaffold allow the photophysical properties of the purine-containing copolymers to be widely varied, with optical bandgaps ranging from 1.96–2.46 eV, and photoluminescent quantum yields as high as ϕ = 0.61. Frontier orbital energy levels determined for the various copolymers using density functional theory tight binding calculations track with experimental results, and the geometric structures of the alkylthiophene-flanked purine monomer and its copolymer are found to be nearly planar. The utility of direct arylation polymerization and intrinsic tailorability of the purine scaffold highlight the potential of these fully conjugated polymers to establish structure–property relationships based on connectivity pattern and comonomer type, which may broadly inform efforts to advance purine-containing conjugated copolymers for various applications.