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Ultrasound acoustic waves are demonstrated to assemble poly-3-hexylthiophene (P3HT) chains into nanofibers after they are fully dissolved in what are commonly considered to be ‘good’ solvents. In the absence of ultrasound, the polymer remains fully dissolved and does not self-assemble for weeks. UV-vis spectroscopy, ultra-small angle X-ray scattering (USAXS) and small angle neutron scattering (SANS) are used to characterize the induced assembly process and to quantify the fraction of polymer that forms nanofibers. It is determined that the solvent type, insonation time, and aging periods are all important factors affecting the structure and final concentration of fibers. The effect of changing polymer regio-regularity, alkyl chain length, and side chain to thiophene ratio are also explored. High intensity focused ultrasound (HIFU) fields of variable intensity are utilized to reveal the physical mechanisms leading to nanofiber formation, which is strongly correlated to cavitation events in the solvent. This in situ HIFU cell, which is designed for simultaneous scattering analysis, is also used to probe for structural changes occurring over multiple length scales using USAXS and SANS. The proposed acoustic assembly mechanism suggests that, even when dispersed in ‘good’ solvents such as bromobenzene, dichlorobenzene and chloroform, P3HT chains are still not in a thermodynamically stable state. Instead, they are stabilized by local energy barriers that slow down and effectively prevent crystallization. Ultrasound fields are found to provide enough mechanical energy to overcome these barriers, triggering the formation of small crystalline nuclei that subsequently seed the growth of larger nanofibers. 

An alkyl-substituted indacenodithiophene-based donor–acceptor π-conjugated polymer ( PIDTBPD ) with low stiffness and high ductility is reported. The polymer was synthesized after DFT calculations predicted that it would have a kinked backbone conformation while showing strong intramolecular charge transfer (ICT), suggestive of the fact that it would be beneficial to the polymer's elasticity and charge mobility. Atom-efficient direct arylation polymerization (DArP) was exploited to synthesize the polymer. Mechanical studies indicate that PIDTBPD has relatively rapid stress-relaxation properties, which lead to a low elastic modulus of 200 MPa and high crack-onset strain of ca . 40% (lower limit). A moderate charge carrier mobility of 2 × 10 −3 cm 2 V −1 s −1 with a current on/off ratio of 2.5 × 10 6 was obtained from the fabricated OFETs. Further experiments were performed to elucidate the structural aspects of this polymer: UV-Vis and PL spectra suggest that minimal conformational change occurs in the polymer between its diluted solution and thin film states; DSC measurements indicate that the polymer's T g is below −20 °C, allowing it to be in a rubbery state at room temperature; and XRD studies support this observation suggesting that the polymer is mostly amorphous at room temperature. 

Abstract Alternating donor–acceptor copolymers are important materials with readily tunable optical and electronic properties. Direct arylation polymerization (DArP) is emerging as an attractive synthetic methodology for the synthesis of these polymers, avoiding the use of prefunctionalized building blocks. However, challenges remain in achieving well‐defined structure, high molecular weight, and impurity‐free polymers. Herein, a study to synthesize three well‐defined donor–acceptor copolymers through DArP is presented. Comparison of¹H NMR and¹³C NMR, as well as optical and electrochemical properties analysis for the polymers and corresponding oligomers provides evidence for the regioregular structure of the polymers. On the basis of the chemical structure of poly(IIDCBT) and the solution electrochemical studies we surmised poly(IIDCBT) could potentially be an electron transport material for organic field‐effect transistors (OFETs), and we determined an electron mobility of 1.2×10⁻³ cm² V⁻¹ s⁻¹for this material.