Unpaired electrons of organic radicals can offer high electrical conductivity without doping, but they typically suffer from low stability. Herein, we report two organic diradicaloids based on quinoidal oligothiophene derivative (QOT), that is, BTICN and QTICN, with high stability and conductivity by employing imide-bridged fused molecular frameworks. The attachment of a strong electron-withdrawing imide group to the tetracyano-capped QOT backbones enables extremely deeply aligned LUMO levels (from −4.58 to −4.69 eV), cross-conjugated diradical characters, and remarkable ambient stabilities of the diradicaloids with half-lives > 60 days, which are among the highest for QOT diradicals and also the widely explored polyaromatic hydrocarbon (PAH)-based diradicals. Specifically, QTICN based on a tetrathiophene imide exhibits a cross-conjugation assisted self-doping in the film state as revealed by XPS and Raman studies. This property in combination with its ordered packing yields a high electrical conductivity of 0.34 S cm −1 for the QTICN films with substantial ambient stability, which is also among the highest values in organic radical-based undoped conductive materials reported to date. When used as an n-type thermoelectric material, QTICN shows a promising power factor of 1.52 uW m −1 K −2 . Our results not only provide new insights into the electron conduction mechanism of the self-doped QOT diradicaloids but also demonstrate the great potential of fused quinoidal oligothiophene imides in developing stable diradicals and high-performance doping-free n-type conductive materials.

Indacenodithiophene (IDT) has been widely used as the central core to design high‐performance acceptor‐donor‐acceptor (A‐D‐A)‐type non‐fullerene acceptors (NFAs). NFAs based on five‐, six‐, seven‐, and nine‐membered IDT have been successfully prepared. However, less research attention has been paid to the eight‐membered IDT derivative. In this study, a novel asymmetric TTPTTT building block as an eight‐membered IDT unit are designed and synthesized. The effect of nonfluorinated, monofluorinated, and difluorinated end‐capping groups on the photovoltaic performance of TTPTTT‐based NFAs are specifically investigated. By blending with the polymer donor PBT1‐C, organic solar cells (OSCs) based on TTPTTT‐IC, TTPTTT‐2F, and TTPTTT‐4F exhibited power conversion efficiencies (PCEs) of 7.91, 11.52, and 12.05%, respectively. Our results indicate that the asymmetric TTPTTT building block as an eight‐membered IDT derivative is a promising central core unit for designing high‐performance A‐D‐A type NFAs.

Electron-deficient ladder-type π-conjugated systems are highly desired for constructing polymer acceptors due to their unique electronic properties. Herein, two series of polymer acceptors PBTIn-(F)T (n = 1-4) based on imidefunctionalized ladder-type heteroarenes (BTIn) with tunable conjugation length are synthesized. Effects of their backbone configuration and electronic properties on film morphology and performance of all-polymer solar cells (all-PSCs) are systematically investigated through theoretical computation, Raman spectroscopy, grazing incidence wide-angle X-ray scattering, etc. It is found that the ladder-type heteroarene size extension and polymer backbone fluorination gradually lower the frontier molecular orbital energy levels, leading to progressive bandgap narrowing with more efficient exciton dissociation. Furthermore, the centrosymmetric and axisymmetric characteristics of BTIn result in distinct backbone configuration with varied self-aggregation and crystalline phases, hence determining the blend film morphology. The highest efficiencies in these two series are attained from PBTI3-T and PBTI3-FT with a curved backbone configuration. PBTI4-(F)T with further extended heteroarenes shows linear backbone, negatively affecting film morphology and efficiency. This study provides fundamental material structure-device performance correlations for ladder-type heteroarenes-based polymer acceptors for the first time and demonstrates that more extended ladder-type backbones do not necessarily improve the device performance, offering guidelines for designing polymer acceptors to maximize all-PSC performance.

We synthesized an A–π–D–π–A‐type nonfullerene small molecule acceptor (Flu‐CNRH) based on fluorene and 2‐(1,1‐dicyanomethylene)rhodanine (CNRH) by a Knoevenagel condensation of the diformyl compound (Flu‐T‐CHO) and CNRH for the use as acceptors in organic photovoltaic cells (OPVs). Introduction of CNRH end groups effectively lowered the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels of the acceptor compared to those of the corresponding rhodanine‐based acceptor (Flu‐RH). The HOMO and LUMO levels of Flu‐CNRH are −5.71 and −3.60 eV, respectively. For comparison, Flu‐RH has HOMO and LUMO energy levels of −5.58 and −3.53 eV, respectively. This lowered LUMO energy level enables Flu‐CNRH to be combined with low bandgap polymer donors PTB7 and PTB7‐Th by providing proper LUMO offsets between donor and acceptor. OPV cells were fabricated with the device configuration of ITO/PEDOT:PSS/active layer/LiF/Al. The best power conversion efficiency of 1.47% was obtained in the P3HT:Flu‐CNRH devices at a D:A ratio of 1:1.5 and with annealing at 140°C. Moreover, Flu‐CNRH showed compatibility with low bandgap polymer donor PTB7 (1.22%) with external quantum efficiency response at a longer wavelength region up to 750 nm, while Flu‐RH had no photovoltaic behavior with PTB7 and PTB7‐Th.