Highly Efficient and Balanced Charge Transport in Thieno[3,4‑<i>c</i>]pyrrole-4,6-dione Copolymers: Dramatic Influence of Thieno[3,2‑<i>b</i>]thiophene Comonomer on Alignment and Charge Transport

The design, synthesis, characterization, and application of a novel series of copolymers based on the electron deficient thieno­[3,4-<i>c</i>]­pyrrole-4,6-dione building block, copolymerized with either thieno­[3,2-<i>b</i>]­thiophene (PTPDTT) or thiophene (PTPDT), are reported. High molecular weights were obtained for PTPDTT via Stille polycondensation. For the PTPDTs, different molecular weights were achieved by varying the polymerization conditions. The increase in molecular weight (PTPDT-2) favors face-on alignment and increases the charge carrier mobility. Grazing-incidence wide-angle X-ray scattering measurements reveal higher crystallinity for PTPDTT with up to 5 orders of lamellar stacking compared to PTPDTs. All polymers show ambipolar charge transport with highly balanced hole and electron mobilities in organic field effect transistors (OFETs), which improve considerably upon thermal annealing. A shift of comonomer from simple thiophene in PTPDT-2 to planar and electron-dense thienothiophene in PTPDTT drastically changes the alignment from face-on to edge-on fashion. Consequently, the charge carrier mobility increases considerably by 1 order of magnitude in PTPDTT, reaching excellent charge carrier mobilities for both holes (0.11 cm² V^–1 s^–1) and electrons (0.17 cm² V^–1 s^–1). PTPDTT was tested as a donor material in combination with PC₇₁BM as well as an acceptor material along with a donor polymer. As a donor material, a power conversion efficiency of 4.3% was reached in combination with PC₇₁BM

Patchy Wormlike Micelles with Tailored Functionality by Crystallization-Driven Self-Assembly: A Versatile Platform for Mesostructured Hybrid Materials

One-dimensional patchy nanostructures are interesting materials due to their excellent interfacial activity and their potential use as carrier for functional nanoparticles. Up to now only wormlike crystalline-core micelles (wCCMs) with a nonfunctional patchy PS/PMMA corona were accessible using crystallization-driven self-assembly (CDSA) of polystyrene-<i>block</i>-polyethylene-<i>block</i>-poly­(methyl methacrylate) (SEM) triblock terpolymers. Here, we present a facile approach toward functional, patchy wCCMs, bearing tertiary amino groups in one of the surface patches. The corona forming PMMA block of a SEM triblock terpolymer was functionalized by amidation with different <i>N</i>,<i>N</i>-dialkyl­ethylene­diamines in a polymer analogous fashion. The CDSA of the functionalized triblock terpolymers in THF was found to strongly depend on the polarity/solubility of the amidated PMMA block. The lower the polarity of the amidated PMMA block (increased solubility), the higher is the accessible degree of functionalization upon which defined, well-dispersed wCCMs are formed. Interestingly, also the structure of the patchy corona can be tuned by the composition/chemistry of the functional patch, giving rise to spherical patches for R = methyl, ethyl and rectangular patches for R = isopropyl. Patchy wCCMs were successfully used as template for the selective incorporation of Au nanoparticles within the amidated corona patches, showing their potential as versatile platform for the construction of functional, mesostructured hybrid materials