Organic semiconducting donor–acceptor polymers are promising candidates for stretchable electronics owing to their mechanical compliance. However, the effect of the electron‐donating thiophene group on the thermomechanical properties of conjugated polymers has not been carefully studied. Here, thin‐film mechanical properties are investigated for diketopyrrolopyrrole (DPP)‐based conjugated polymers with varying numbers of isolated thiophene moieties and sizes of fused thiophene rings in the polymer backbone. Interestingly, it is found that these thiophene units act as an antiplasticizer, where more isolated thiophene rings or bigger fused rings result in an increased glass transition temperature (Tg) of the polymer backbone, and consequently elastic modulus of the respective DPP polymers. Detailed morphological studies suggests that all samples show similar semicrystalline morphology. This antiplasticization effect also exists in para‐azaquinodimethane‐based conjugated polymers, indicating that this can be a general trend for various conjugated polymer systems. Using the knowledge gained above, a new DPP‐based polymer with increased alkyl side chain density through attaching alky chains to the thiophene unit is engineered. The new DPP polymer demonstrates a record low Tg, and 50% lower elastic modulus than a reference polymer without side‐chain decorated on the thiophene unit. This work provides a general design rule for making low‐Tg conjugated polymers for stretchable electronics.

This work examines an additive approach that increases dielectric screening to overcome performance challenges in organic shortwave infrared (SWIR) photodiodes. The role of the high-permittivity additive, camphoric anhydride, in the exciton dissociation and charge collection processes is revealed through measurements of transient photoconductivity and electrochemical impedance. Dielectric screening reduces the exciton binding energy to increase exciton dissociation efficiency and lowers trap-assisted recombination loss, in the absence of any morphological changes for two polymer variants. In the best devices, the peak internal quantum efficiency at 1100 nm is increased up to 66%, and the photoresponse extends to 1400 nm. The SWIR photodiodes are integrated into a 4 × 4 pixel imager to demonstrate tissue differentiation and estimate the fat-to-muscle ratio through noninvasive spectroscopic analysis.

Conductive polymers largely derive their electronic functionality from chemical doping, processes by which redox and charge‐transfer reactions form mobile carriers. While decades of research have demonstrated fundamentally new technologies that merge the unique functionality of these materials with the chemical versatility of macromolecules, doping and the resultant material properties are not ideal for many applications. Here, it is demonstrated that open‐shell conjugated polymers comprised of alternating cyclopentadithiophene and thiadiazoloquinoxaline units can achieve high electrical conductivities in their native “undoped” form. Spectroscopic, electrochemical, electron paramagnetic resonance, and magnetic susceptibility measurements demonstrate that this donor–acceptor architecture promotes very narrow bandgaps, strong electronic correlations, high‐spin ground states, and long‐range π‐delocalization. A comparative study of structural variants and processing methodologies demonstrates that the conductivity can be tuned up to 8.18 S cm−1. This exceeds other neutral narrow bandgap conjugated polymers, many doped polymers, radical conductors, and is comparable to commercial grades of poly(styrene‐sulfonate)‐doped poly(3,4‐ethylenedioxythiophene). X‐ray and morphological studies trace the high conductivity to rigid backbone conformations emanating from strong π‐interactions and long‐range ordered structures formed through self‐organization that lead to a network of delocalized open‐shell sites in electronic communication. The results offer a new platform for the transport of charge in molecular systems.

NIR-SWIR photoresponsive donor–acceptor polymers enable the detection of infrared light when incorporated into bulk heterojunction photodiodes.

IntroductionSupercapacitors are electrochemical energy storage devices that store charge through fast, reversible redox reactions, enable load-leveling, regenerative energy harvesting, and high power applications. [1][2][3][4][5][6] The energy density of a supercapacitor (E = CV 2 /2) is linearly dependent on the specific capacitance C and proportional to the square of the operational voltage V. The main strategies to increase energy depend upon the mechanism of charge storage, whether capacitive or Faradaic. Capacitive electrodes store charge on the surface; hence, research is focused on strategies to increase the surface area, typically based on high surface area carbons. [7][8][9] Faradaic materials undergo redox reactions and offer the ability to tune the operating voltage. There has been considerable success in tuning the cathode voltage and delivering high capacitance systems operating at the upper limit of prototypical nonaqueous electrolytes. [1,7] However, the device voltage and energy remain limited by a lack of complementary high power electrodes for the anode. [10,11] In the absence of new high voltage electrolytes, there is no room to further extend the cathode potential, because over-potential may lead to hazardous runaway reactions between the highly oxidized cathodes and flammable nonaqueous electrolytes. In contrast, it is generally safe for nonaqueous electrolytes to operate down to −2 V relative to the Ag/AgCl electrode, and the development of anode materials is critical to increase the energy densities of supercapacitors.Consequently, there is an urgent need for strategies aimed at extending the operational voltage toward negative potentials to improve the energy density and cell voltage of supercapacitors. As an alternative to metal oxides, redox-active macromolecules offer mechanical flexibility, low-cost, and scalability relevant for small and large scale applications. [12][13][14][15][16] In radical polymers, [17][18][19][20] the redox sites are at pendant radical groups distributed along a polymer backbone. Due to the insulating nature of the backbone and low conductivity, devices based on these materials require blending with additional conductive materials for electron transport, ultimately lowering the electrode energy Supercapacitors have emerged as an important energy storage technology offering rapid power delivery, fast charging, and long cycle lifetimes. While extending the operational voltage is improving the overall energy and power densities, progress remains hindered by a lack of stable n-type redox-active materials. Here, a new Faradaic electrode material comprised of a narrow bandgap donor−acceptor conjugated polymer is demonstrated, which exhibits an open-shell ground state, intrinsic electrical conductivity, and enhanced charge delocalization in the reduced state. These attributes afford very stable anodes with a coulombic efficiency of 99.6% and that retain 90% capacitance after 2000 charge-discharge cycles, exceeding other n-dopable organic materials. Redox cycling proce...