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Despite the outstanding electric properties and cost-effectiveness of poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives, their performance as hole transport layer (HTL) materials in conventional perovskite solar cells (PSCs) has lagged behind that of widely used spirobifluorene-based molecules or poly(triaryl amine). This gap is mainly from their poor solubility and energy alignment mismatch. In this work, the design and synthesis of a pyrrole-modified HTL (PPr) based on 3,4-propylenedioxythiophene (ProDOT) are presented for efficient and stable PSCs. As a result of the superior defects passivation ability, excellent contact with perovskite, enhanced hole extraction, and high hydrophobicity, the unencapsulated PPr-based PSCs showed the peak PCE of 21.49% and outstanding moisture stability (over 4000 h). This work highlights the potential application of ProDOT-based materials as HTL for PSCs and underscores the importance of the rational design of PEDOT and its derivatives., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

The recent discovery of highly conductive, solution-processable, n-doped poly(benzodifurandione) (n-PBDF) marks a milestone in the development of conducting polymers. Currently, n-PBDF is prepared by either duroquinone-mediated or copper-catalyzed polymerizations, where scalability and cost-effectiveness may present challenges. Here, we report a general, scalable, and cost-effective method for n-PBDF and its derivatives, namely selenium dioxide (SeO2) catalyzed polymerization. We discovered that a catalytic amount of selenium dioxide leads to high monomer conversions (>99% by NMR). The obtained n-PBDF exhibits a consistently narrow hydrodynamic diameter distribution and its thin films show high conductivities. Furthermore, we revealed that this polymerization involves a mechanism distinct from the previously reported radical pathway. It involves successive Riley oxidation and aldol polycondensation processes. It was also found that the reduced selenium precipitates from dimethyl sulfoxide (DMSO) when the catalytic cycle is terminated, allowing for a straightforward purification process through centrifugation and filtration. This method thus eliminates the need for the costly and slow dialysis process. Finally, we demonstrated that SeO2 catalyzed polymerization is applicable to n-PBDF derivatives, proving the generality of this method., (© 2024 Wiley‐VCH GmbH.)

Recently, solution-processable n-doped poly(benzodifurandione) (n-PBDF) has been made through in-situ oxidative polymerization and reductive doping, which exhibited exceptionally high electrical conductivities and optical transparency. The discovery of n-PBDF is considered a breakthrough in the field of organic semiconductors. In the initial report, the possibility of structural defect formation in n-PBDF was proposed, based on the observation of structural isomerization from (E)-2H,2'H-[3,3'-bibenzofuranylidene]-2,2'-dione (isoxindigo) to chromeno[4,3-c]chromene-5,11-dione (dibenzonaphthyrone) in the dimer model reactions. In this study, we present clear evidence that structural isomerization is inhibited during polymerization. We reveal that the dimer (BFD1) and the trimer (BFD2) can be reductively doped by several mechanisms, including hydride transfer, forming charge transfer complexes (CTC) or undergoing an integer charge transfer (ICT) with reactants available during polymerization. Once the hydride transfer adducts, the CTC, or the ICT product forms, structural isomerization can be effectively prevented even at elevated temperatures. Our findings provide a mechanistic understanding of why isomerization-derived structural defects are absent in n-PBDF backbone. It lays a solid foundation for the future development of n-PBDF as a benchmark polymer for organic electronics and beyond., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The interaction between light and chiroptical polymers plays a crucial role in chiroptics, spintronics, and chiral-spin selectivity. Despite considerable successes in creating dissymmetric polymer films, the elucidation of chiroptical activities under electrochemical switching remains unexplored. Here homogeneous chiral electrochromics is reported using chiral assembly of conjugated polymers through a transient solidification process with molecular chiral templates. In their neutral state, the chiral electrochromic polymers directly produce a remarkably dissymmetric polarization-dependent transmittance. The circular dichroism (CD) and dissymmetric transmission can be tuned by adjusting the doping level of the electrochemically active polymer films. Under high levels of oxidation, the chiroptical activities are reversed with strong bleaching in the visible, leading to formation of monosignate CD spectra over the infrared region. The matching between circular polarization handedness and chirality of chiroptical polymers makes a distinct impact on optical contrast and color switching dynamics due to the flipped chiroptical activities through polymer redox reactions. The differential circularly polarized transmission in the chiral see-through display can make a well-resolved color change in human eyes, demonstrating proof-of-concept devices for 3D imaging and information encryption. This work serves as a foundation to develop advanced on-chip fabrication of circular polarization-multiplexed display in flexible and highly integrated platforms., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Perovskite solar cells (PSCs) have delivered a power conversion efficiency (PCE) of more than 25% and incorporating polymers as hole-transporting layers (HTLs) can further enhance the stability of devices toward the goal of commercialization. Among the various polymeric hole-transporting materials, poly(triaryl amine) (PTAA) is one of the promising HTL candidates with good stability; however, the hydrophobicity of PTAA causes problematic interfacial contact with the perovskite, limiting the device performance. Using molecular side-chain engineering, a uniform 2D perovskite interlayer with conjugated ligands, between 3D perovskites and PTAA is successfully constructed. Further, employing conjugated ligands as cohesive elements, perovskite/PTAA interfacial adhesion is significantly improved. As a result, the thin and lateral extended 2D/3D heterostructure enables as-fabricated PTAA-based PSCs to achieve a PCE of 23.7%, improved from the 18% of reference devices. Owing to the increased ion-migration energy barrier and conformal 2D coating, unencapsulated devices with the new ligands exhibit both superior thermal stability under 60 °C heating and moisture stability in ambient conditions., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Surface passivation is an effective way to boost the efficiency and stability of perovskite solar cells (PSCs). However, a key challenge faced by most of the passivation strategies is reducing the interface charge recombination without imposing energy barriers to charge extraction. Here, a novel multifunctional semiconducting organic ammonium cationic interface modifier inserted between the light-harvesting perovskite film and the hole-transporting layer is reported. It is shown that the conjugated cations can directly extract holes from perovskite efficiently, and simultaneously reduce interface non-radiative recombination. Together with improved energy level alignment and the stabilized interface in the device, a triple-cation mixed-halide medium-bandgap PSC with an excellent power conversion efficiency of 22.06% (improved from 19.94%) and suppressed ion migration and halide phase segregation, which lead to a long-term operational stability, is demonstrated. This strategy provides a new practical method of interface engineering in PSCs toward improved efficiency and stability., (© 2021 Wiley-VCH GmbH.)

The electrochromism of a water-soluble naturally oxidized electrochromic polymer, ox-PPE, is harnessed for rapid and facile bacterial detection, discrimination, and susceptibility testing. The ox-PPE solution shows distinct colorimetric and spectroscopic changes within 30 min when mixed with live bacteria. For the underlying mechanism, it is found that ox-PPE responds to the reducing species (e.g. cysteine and glutathione) released by metabolically active bacteria. This reduction reaction is ubiquitous among various bacterial strains, with a noticeable difference that enables discrimination of Gram-negative and Gram-positive bacterial strains. Combining ox-PPE with antibiotics, methicillin-susceptible and -resistant S. aureus can be differentiated within 2.5 h. Proof-of-concept demonstration of ox-PPE for antimicrobial susceptibility testing is carried out by incubating E. coli with various antibiotics. The obtained minimum inhibition concentrations are consistent with the conventional culture-based methods, but with the procedure time significantly shortened to 3 h.

The design of functional interfaces is central to both fundamental and applied research in materials science and energy technology. We introduce a new, broadly applicable technique for the precisely controlled high-throughput preparation of well-defined interfaces containing polyatomic species ranging from small ions to nanocrystals and large protein complexes. The mass-dispersive deposition of ions onto surfaces is achieved using a rotating-wall mass analyzer, a compact device which enables the separation of ions using low voltages and has a theoretically unlimited mass range. We demonstrate an efficient deposition of singly charged Au 144 (SC 4 H 9 ) 60 ions (33.7 kDa), which opens up exciting opportunities for the structural characterization of nanocrystals and their assemblies using transmission electron microscopy. Our approach also enables the high-throughput deposition of mass-selected ions from multicomponent mixtures, which is of interest to the controlled preparation of surface gradients and rapid screening of molecules in mixtures for a specific property., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Development of molecular probes holds great promise for early diagnosis of aggressive prostate cancer. Here, 2-[3-(1,3-dicarboxypropyl) ureido] pentanedioic acid (DUPA)-conjugated ligand and bis-isoindigo-based polymer (BTII) are synthesized to formulate semiconducting polymer nanoparticles (BTII-DUPA SPN) as a prostate-specific membrane antigen (PSMA)-targeted probe for prostate cancer imaging in the NIR-II window. Insights into the interaction of the imaging probes with the biological targets from single cell to whole organ are obtained by transient absorption (TA) microscopy and photoacoustic (PA) tomography. At single-cell level, TA microscopy reveals the targeting efficiency, kinetics, and specificity of BTII-DUPA SPN to PSMA-positive prostate cancer. At organ level, PA tomographic imaging of BTII-DUPA SPN in the NIR-II window demonstrates superior imaging depth and contrast. By intravenous administration, BTII-DUPA SPN demonstrates selective accumulation and retention in the PSMA-positive tumor, allowing noninvasive PA detection of PSMA overexpressing prostate tumors in vivo. The distribution of nanoparticles inside the tumor tissue is further analyzed through TA microscopy. These results collectively demonstrate BTII-DUPA SPN as a promising probe for prostate cancer diagnosis by PA tomography., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Thienoisoindigo-based semiconducting polymer with a strong near-infrared absorbance is synthesized and its water-dispersed nanoparticles (TSPNs) are investigated as a contrast agent for photoacoustic (PA) imaging in the second near-infrared (NIR-II) window (1000-1350 nm). The TSPNs generate a strong PA signal in the NIR-II optical window, where background signals from endogenous contrast agents, including blood and lipid, are at the local minima. By embedding a TSPN-containing tube in chicken-breast tissue, an imaging depth of more than 5 cm at 1064 nm excitation is achieved with a contrast-agent concentration as low as 40 µg mL -1 . The TSPNs under the skin or in the tumor are clearly visualized at 1100 and 1300 nm, with negligible interference from the tissue background. TSPN as a PA contrast in the NIR-II window opens new opportunities for biomedical imaging of deep tissues with improved contrast., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Melt-processing of complementary semiconducting polymer blends provides an average charge carrier mobility of 0.4 cm 2 V -1 s -1 and current on/off ratios higher than 10 5 , a record performance for melt-processed organic field-effect transistors., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Increasing the flexibility of polymer chains is a common method of increasing the deformability of solid polymeric materials. Here, the effects of "conjugation-break spacers" (CBSs)-aliphatic units that interrupt the sp 2 -hybridized backbone of semiconducting polymers-on the mechanical and photovoltaic properties of a diketopyrrolopyrrole-based polymer are described. Unexpectedly, the tensile moduli and cracking behavior of a series of polymers with repeat units bearing 0%, 30%, 50%, 70%, and 100% of the CBS are not directly related to the percent incorporation of the flexible unit. Rather, the mechanical properties are a strong function of the order present in the film as determined by grazing-incidence x-ray diffraction. The effect of the CBSs on the photovoltaic performance of these materials, on the other hand, is more intuitive: it decreases with increasing fraction of the flexible units. These studies highlight the importance of solid-state packing structure-as opposed to only the flexibility of the individual molecules-in determining the mechanical properties of a conjugated polymer film for stretchable, ultraflexible, and mechanically robust electronics., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Diketopyrrolopyrrole-based semiconducting polymer nanoparticles with high photostability and strong photoacoustic brightness are designed and synthesized, which results in 5.3-fold photoacoustic signal enhancement in tumor xenografts after systemic administration., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The use of second-generation [(NHC)Pd(R-allyl)Cl] complexes for Suzuki-Miyaura and Buchwald-Hartwig cross-coupling reactions involving heteroaromatic halides at room temperature is reported. The first examples of room temperature Suzuki-Miyaura cross-coupling of deactivated aryl chlorides with alkenyl boronic acids are also disclosed. Terminal substitution at the allyl moiety of the palladium complex facilitates its activation at room temperature leading to very active catalytic species enabling the present catalytic transformations to be performed rapidly using very mild reaction conditions. Catalyst loadings can be as low as 10 ppm for the Buchwald-Hartwig aryl amination and 50 ppm for the Suzuki-Miyaura reaction.