Back Cover: Defect‐Free Alternating Conjugated Polymers Enabled by Room‐ Temperature Stille Polymerization (Angew. Chem. Int. Ed. 16/2022)

Abstract

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).

Stille type P–C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution

“…Previous mechanistic studies of Stille C-C coupling reaction provided a base for the possible mechanism of P-C coupling reaction. [46][47][48][49][50][51][52][53][54] The plausible reaction pathway is shown in Figure 1a. We also calculated the free energy changes by using density functional theory (DFT) calculations (see the details in SI).…”

The Aryl Sulfide Synthesis via Sulfide Transfer

“…This observation suggested the non‐radiative decay route may be efficient in 5 ‐based organic/polymeric semiconductors [33] . Thus, 5 was copolymerized with ditrimethylstannyl‐diketopyrrolopyrrole units to afford the copolymer P1 in excellent yield via a room temperature Stille coupling [34] . The P1 solution exhibited a broad and strong absorption (λ max = 666 nm) in the first near‐infrared (NIR−I) region, while nanoparticles (NPs) demonstrated an obvious red‐shifted absorption with the absorption peak at 708 nm (Figure 3a).…”

“…[33] Thus, 5 was copolymerized with ditrimethylstannyl-diketopyrrolopyrrole units to afford the copolymer P1 in excellent yield via a room temperature Stille coupling. [34] The P1 solution exhibited a broad and strong absorption (λ max = 666 nm) in the first near-infrared (NIRÀ I) region, while nanoparticles (NPs) demonstrated an obvious red-shifted absorption with the absorption peak at 708 nm (Figure 3a). Next, the photothermal effect of P1 nanoparticles (NPs) was investigated.…”

Nickel‐Catalyzed Direct Arylation Polymerization for the Synthesis of Thiophene‐Based Cross‐linked Polymers

“…Advantageously avoiding the homocoupling reaction, this Ni‐catalyzed C−H arylation would allow for alternating units though orthogonal synthesis strategy to prepare periodic, sequential conjugated copolymers. Such perfectly alternating conjugated polymers, without homocoupling pattern affecting light absorption and charge transport, are of a great interest for semiconductors and optoelectronics [26–30] . Furthermore, to introduce porosity within such polymeric networks, we envisioned alternating di‐/tritopic heteroarenes and tri‐/tetratopic (hetero)aryl electrophiles to get three dimensional polymeric frameworks with intrinsic porosity (Scheme 1b).…”

“…Such perfectly alternating conjugated polymers, without homocoupling pattern affecting light absorption and charge transport, are of a great interest for semiconductors and optoelectronics. [26][27][28][29][30] Furthermore, to introduce porosity within such polymeric networks, we envisioned alternating di-/tritopic heteroarenes and tri-/tetratopic (hetero)aryl electrophiles to get three dimensional polymeric frameworks with intrinsic porosity (Scheme 1b).…”