Defect‐free alternating conjugated polymers were produced by exploring palladium‐catalyzed Stille polymerization at room temperature. The selected copolymers demonstrated no homocoupling defects and superior charge transport properties, thus paving the road for the development of plastic electronics. Details of this study are reported by Qinqin Shi, Hui Huang, and co‐workers in their Research Article (e202115969).
The Stille cross‐coupling polymerization is one of the most efficient synthetic methods for donor–acceptor (D–A) type π‐conjugated polymers (CPs). Nevertheless, thermal‐activation Stille polymerization readily produced homocoupling defects, resulting in batch‐to‐batch variations in copolymers quality and deteriorating the device performance of electronics and optoelectronics. Here, a room‐temperature Stille‐type polymerization was developed, the utility and generality of which were demonstrated by synthesis of twelve D–A CPs with high molecular weights. Importantly, the resultant copolymers possessed no homocoupling (hc) structural defects, while hc reactions were observed in the thermal‐activation Stille reactions. Thus, the organic field‐effect transistors (OFETs) based on the former exhibited twofold higher charge transport mobility (2.10 cm2 V−1 s−1), since it possessed stronger crystallinity and lower trap density of states (tDOS).
Aryl sulfides are in great demands in drugs and materials sciences. To avoid using nucleophilic and noxious thiols, many efforts have been focused on exploring novel sulfide resources. Herein, a reductive Pd-catalyzed, Ni-mediated method to synthesize aryl sulfides via a sulfide transfer reaction is developed. The utility and scope of this reaction is exemplified by various aryl electrophiles and aryl sulfides.Mechanistic studies reveal two competing catalytic cycles of sulfide transfer and aryl transfer in this reaction, where the former one is favored over the later one because of the large energy barrier difference during the transmetalation. Moreover, two important chemicals are late-stage functionalized by this method, exhibiting the potential applications in drugs and materials science.
The Stille cross-coupling polymerization is one of the most efficient synthetic methods for donoracceptor (D-A) type π-conjugated polymers (CPs). Nevertheless, thermal-activation Stille polymerization readily produced homocoupling defects, resulting in batch-to-batch variations in copolymers quality and deteriorating the device performance of electronics and optoelectronics. Here, a room-temperature Stille-type polymerization was developed, the utility and generality of which were demonstrated by synthesis of twelve D-A CPs with high molecular weights. Importantly, the resultant copolymers possessed no homocoupling (hc) structural defects, while hc reactions were observed in the thermal-activation Stille reactions. Thus, the organic field-effect transistors (OFETs) based on the former exhibited twofold higher charge transport mobility (2.10 cm 2 V À 1 s À 1 ), since it possessed stronger crystallinity and lower trap density of states (tDOS).
…a lternierende konjugierte Polymere wurden durch Pd-katalysierte Stille-Polymeribei Raumtemperatur hergestellt. Die ausgewählten Copolymere weisen keine Homokupplungsdefekte auf und zeigen hervorragende Ladungstransporteigenschaften, was einen Wegfürd ie Entwicklung von Kunststoffelektronik aufzeigt. Einzelheiten zu dieser Studie werden im Forschungsartikel von Qinqin Shi, Hui Huang et al. erläutert (e202115969).
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