Perylene Bisimide-Functionalized Triphenylmethyl Radicals Showing High Stability and Reversible Electrochemical Redox Properties.

This study presents a series of triphenylmethyl monoradicals incorporating varying numbers of peripheral perylene bisimide (PBI) substituents (1PBI-TTM·, 2PBI-TTM· and 3PBI-TTM·). The incorporation of electron-withdrawing PBI substituents significantly enhances the stability of these carbon radicals, enabling them to display exceptional electrochemical redox reversibility. Notably, the electronic interplay between the PBI substituents and the central triphenylmethyl core facilitates unique and reversible multi-step redox reactions. Among the reported redicals, the tris-PBI functionalized radical (3PBI-TTM·) demonstrates the remarkable ability to accommodate up to seven electrons under negative potentials, forming high valence anions. This research pioneers the development of highly stable carbon radicals with superior electrochemical oxidation-reduction processes, presenting promising avenues for the advancement of electric energy storage technologies.

Extremely Stable Perylene Bisimide-Bridged Regioisomeric Diradicals and Their Redox Properties.

Excellent stability is an essential premise for organic diradicals to be used in organic electronic and spintronic devices. We have attached two tris(2,4,6-trichlorophenyl)methyl (TTM) radical building blocks to the two sides of perylene bisimide (PBI) bridges and obtained two regioisomeric diradicals (1,6-TTM-PBI and 1,7-TTM-PBI). Both of the isomers show super stability rather than the monomeric TTM under ambient conditions, due to the increased conjugation and the electron-withdrawing effects of the PBI bridges. The diradicals show distinct and reversible multistep redox processes, and a spectro-electrochemistry investigation revealed the generation of organic mixed-valence (MV) species during reduction processes. The two diradicals have singlet ground states, very small singlet-triplet energy gaps (ΔES-T ) and a pure open-shell character (with diradical character y0 =0.966 for 1,6-TTM-PBI and 0.967 for 1,7-TTM-PBI). This work opens a window to developing very stable diradicals and offers the opportunity of their further application in optical, electronic and magnetic devices.

Fluorescence Modulation through the Inverted Energy Gap Law in Triply N─B←N-Containing Windmill-Shaped Triazines.

A series of windmill-shape heterocyclic molecules containing three N─B←N units, TBN and its derivatives, with quasi-planar C3 symmetric backbone, are synthesized. The parent TBN exhibits a strongly allowed, doubly degenerate lowest excited state but suffers from very low fluorescence, due to very fast nonradiative decay rate through a conical intersection (CI) as revealed by femtosecond transient absorption spectroscopy and quantum-chemical calculations. Introducing peripheral phenyl- or thienyl-groups (Ph-TBN or Th-TBN) induces pronounced bathochromic shifts and enhances fluorescence, which is beneficial from inhibited nonradiative pathway by the increased energy barriers to access the CI at excited state. The understanding of this rather uncommon behaviour may open routes for the design of novel fluorescence materials.

Unraveling the Role of Non-Fullerene Acceptor with High Dielectric Constant in Organic Solar Cells.

Increasing the relative dielectric constant is a constant pursuit of organic semiconductors, but it often leads to multiple changes in device characteristics, hindering the establishment of a reliable relationship between dielectric constant and photovoltaic performance. Herein, a new non-fullerene acceptor named BTP-OE is reported by replacing the branched alkyl chains on Y6-BO with branched oligoethylene oxide chains. This replacement successfully increases the relative dielectric constant from 3.28 to 4.62. To surprise, BTP-OE offers consistently lower device performance relative to Y6-BO in organic solar cells (16.27% vs 17.44%) due to the losses in open-circuit voltage and fill factor. Further investigations unravel that BTP-OE has resulted in reduced electron mobility, increased trap density, enhanced first order recombination, and enlarged energetic disorder. These results demonstrate the complex relationship between dielectric constant and device performance, which provide valuable implications for the development of organic semiconductors with high dielectric constant for photovoltaic application.

Boron-Locked Starazine - A Soluble and Fluorescent Analogue of Starphene.

A starlike heterocyclic molecule containing an electron-deficient nonaaza-core structure and three peripheral isoquinolines locked by three tetracoordinate borons, namely isoquinoline-nona-starazine (QNSA), is synthesized by using readily available reactants through a rather straightforward approach. This new heteroatom-rich QNSA possesses a quasi-planar π-backbone structure, and bears phenyl substituents on borons which protrude on both sides of the π-backbones endowing it with good solubility in common organic solvents. Contrasting to its starphene analogue, QNSA shows intense fluorescence with a quantum yield (PLQY) of up to 62 % in dilute solution.

Simple Non-Fused Electron Acceptors Leading to Efficient Organic Photovoltaics.

Despite the remarkable progress achieved in recent years, organic photovoltaics (OPVs) still need work to approach the delicate balance between efficiency, stability, and cost. Herein, two fully non-fused electron acceptors, PTB4F and PTB4Cl, are developed via a two-step synthesis from single aromatic units. The introduction of a two-dimensional chain and halogenated terminals for these non-fused acceptors plays a synergistic role in optimizing their solid stacking and orientation, thus promoting an elongated exciton lifetime and fast charge-transfer rate in bulk heterojunction blends. As a result, PTB4Cl, upon blending with PBDB-TF polymer, has enabled single-junction OPVs with power conversion efficiencies of 12.76 %, representing the highest values among the reported fully unfused electron acceptors so far.

Synthetic Routes for Heteroatom-Containing Alkylated/Arylated Polycyclic Aromatic Hydrocarbons.

Synthetic routes for heteroatom-containing polycyclic aromatic hydrocarbons (H-PAHs) with alkyl and aryl substitution are demonstrated. Three H-PAHs, including heteroatom-containing rubicenes (H-rubicenes), angular-benzothiophenes (ABTs), and indenothiophene (IDTs) were successfully synthesized by two key steps, including polysubstituted olefin formation and cyclization. Specifically, ABT and H-rubicenes were comprehensively investigated by single-crystal X-ray diffraction, NMR spectroscopy, UV-vis absorption, cyclic voltammetry, transient absorption, and single-crystal OFET measurements.

Butterfly Effects Arising from Starting Materials in Fused-Ring Electron Acceptors.

We designed and synthesized a series of fused-ring electron acceptors (FREAs) based on naphthalene-fused octacyclic cores end-capped by 3-(1,1-dicyanomethylene)-5,6-difluoro-1- indanone (NOICs) using a bottom-up approach. The NOIC series shares the same end groups and side chains, as well as similar fused-ring cores. The butterfly effects, arising from different methoxy positions in the starting materials, impact the design of the final FREAs, as well as their molecular packing, optical and electronic properties, charge transport, film morphology, and performance of organic solar cells. The binary-blend devices based on this NOIC series show power conversion efficiencies varying from 7.15% to 14.1%, due to the different intrinsic properties of the NOIC series, morphologies of blend films, and voltage losses of devices.

Consecutive Charging of a Perylene Bisimide Dye by Multistep Low-Energy Solar-Light-Induced Electron Transfer Towards H2 Evolution.

A photocatalytic system containing a perylene bisimide (PBI) dye as a photosensitizer anchored to titanium dioxide (TiO2 ) nanoparticles through carboxyl groups was constructed. Under solar-light irradiation in the presence of sacrificial triethanolamine (TEOA) in neutral and basic conditions (pH 8.5), a reaction cascade is initiated in which the PBI molecule first absorbs green light, giving the formation of a stable radical anion (PBI.- ), which in a second step absorbs near-infrared light, forming a stable PBI dianion (PBI2- ). Finally, the dianion absorbs red light and injects an electron into the TiO2 nanoparticle that is coated with platinum co-catalyst for hydrogen evolution. The hydrogen evolution rates (HERs) are as high as 1216 and 1022 µmol h-1 g-1 with simulated sunlight irradiation in neutral and basic conditions, respectively.

High Exciton Diffusion Coefficients in Fused Ring Electron Acceptor Films.

Modest exciton diffusion lengths dictate the need for nanostructured bulk heterojunctions in organic photovoltaic (OPV) cells; however, this morphology compromises charge collection. Here, we reveal rapid exciton diffusion in films of a fused-ring electron acceptor that, when blended with a donor, already outperforms fullerene-based OPV cells. Temperature-dependent ultrafast exciton annihilation measurements are used to resolve a quasi-activationless exciton diffusion coefficient of at least 2 × 10-2 cm2/s, substantially exceeding typical organic semiconductors and consistent with the 20-50 nm domain sizes in optimized blends. Enhanced three-dimensional diffusion is shown to arise from molecular and packing factors; the rigid planar molecular structure is associated with low reorganization energy, good transition dipole moment alignment, high chromophore density, and low disorder, all enhancing long-range resonant energy transfer. Relieving exciton diffusion constraints has important implications for OPVs; large, ordered, and pure domains enhance charge separation and transport, and suppress recombination, thereby boosting fill factors. Further enhancements to diffusion lengths may even obviate the need for the bulk heterojunction morphology.

Tetrahydroxy-Perylene Bisimide Embedded in a Zinc Oxide Thin Film as an Electron-Transporting Layer for High-Performance Non-Fullerene Organic Solar Cells.

By introduction of four hydroxy (HO) groups into the two perylene bisimide (PBI) bay areas, new HO-PBI ligands were obtained which upon deprotonation can complex ZnII ions and photosensitize semiconductive zinc oxide thin films. Such coordination is beneficial for dispersing PBI photosensitizer molecules evenly into metal oxide films to fabricate organic-inorganic hybrid interlayers for organic solar cells. Supported by the photoconductive effect of the ZnO:HO-PBI hybrid interlayers, improved electron collection and transportation is achieved in fullerene and non-fullerene polymer solar cell devices, leading to remarkable power conversion efficiencies of up to 15.95 % for a non-fullerene based organic solar cell.

Converting Thioether Waste into Organic Semiconductors by Carbon-Sulfur Bond Activation.

A goal for human society is to convert organic waste into valuable materials. Herein, 2-(methylthio)-bezothiazole (MTBT), an important organic waste in urban runoff, was catalytically converted into a series of organic semiconductors through carbon-sulfur bond activation. The efficient conversion of various substrates with different aromatic moieties and reacting functional groups (tin and boron) proved the generality of this novel diarylation Liebeskind-Srogl methodology. Moreover, the resulting organic semiconductors showed excellent performance in field effect transistors and cell imaging. This contribution presents an excellent example of converting organic waste into valuable materials and may open a new avenue to utilizing widely available aromatic thioethers.

Two-Dimensional Ruddlesden-Popper Perovskite with Nanorod-like Morphology for Solar Cells with Efficiency Exceeding 15.

Two-dimensional (2D) Ruddlesden-Popper perovskites have shown great potential for application in perovskite solar cells due to their appealing environmental stability. However, 2D perovskites generally show poor photovoltaic performance. Here, a new type of 2D perovskite using 2-thiophenemethylammonium (ThMA+) as a spacer cation was developed and high photovoltaic performance as well as enhanced stability in comparison with its 3D counterpart was demonstrated. The use of the 2D perovskite (ThMA)2(MA) n-1Pb nI3 n+1 ( n = 3) in deposited highly oriented thin films from N, N-dimethylformamide using a methylammonium chloride (MACl) assisted film-forming technique dramatically improves the efficiency of 2D perovskite photovoltaic devices from 1.74% to over 15%, which is the highest efficiency for 2D perovskite ( n < 6) solar cells so far. The enhanced performance of the 2D perovskite devices using MACl as additive is ascribed to the growth of a dense web of nanorod-like film with near-single-crystalline quality, in which the crystallographic planes of the 2D MA n-1Pb nI3 n+12- slabs preferentially aligned perpendicular to the substrate, thus facilitating efficient charge transport. This work provides a new insight into exploration of the formation mechanism of 2D perovskites with increased crystallinity and crystal orientation suitable for high-performance solar cells.

Light-activated electric bistability for evaporated silver nanoparticles in organic field-effect transistors.

Evaporated naked silver nanoparticles (Ag-NPs) were embedded in the isolated layer of PTB7-based organic field-effect transistors (OFETs), where their electric bistability behavior was successfully activated by photo-irradiation. These devices showed no obvious memory behavior in the dark; while under weak photo-irradiation (0.015 mW cm-2), memory windows of 12.5-35 V have been achieved. Different operation modes have been designed to exhibit the memory behavior and to explore the origin of the formation of a stable charge state. The immobilized photo-generated electrons supplied an additional photo-generated electric field, which confined the trapped charge in the charge storage media after the gate voltage and photo-irradiation being removed. The photo-irradiation created more charges at the interface, and the presence of Ag-NPs allowed effective charge storage of the majority carriers, which increased the drain current and lowered the gate-operating voltage. This method is a novel approach to light-activated electric bistability based charge storage.

Electrochemical Deposition of Azobenzene-Containing Network Films with High-Contrast and Stable Photoresponse.

To fabricate stable photoresponsive films and devices, a cross-linked network that firmly fixes the position of the chromophores is an ideal structure, because aggregation and/or phase separation effects of chromophores in matrix can be effectively restrained in such robust films. Herein, the in situ electrochemical deposition (ED) of azo-based precursors containing multielectroactive carbazole units is utilized to construct highly cross-linked photoresponsive films. 2-(4-(9,9-bis(6-(9H-carbazol-9-yl)hexyl)-9H-fluoren-2-yl)phenyl)-1-(4-(9,9-bis(6-(9H-carbazol-9-yl)hexyl)-9H-fluoren-7-yl)phenyl)diazene (BFCzAzo) with high solvability in electrolyte solution, high electroactivity, and highly efficient photoresponsive ability is synthesized by Suzuki coupling reaction as a kind of ED precursor. A highly cross-linked photoresponsive film is fabricated by ED method using BFCzAzo as ED precursor. The film can be patterned in large area by irradiation with interfering laser beam (355 nm), and the pattern possesses excellent thermal stability and insoluble ability in both organic and inorganic solvents. Excellent reversibility of the nanostructures is demonstrated by irradiation with 550 nm laser beam.

Photoconductive Cathode Interlayer for Highly Efficient Inverted Polymer Solar Cells.

A highly photoconductive cathode interlayer was achieved by doping a 1 wt % light absorber, such as perylene bisimide, into a ZnO thin film, which absorbs a very small amount of light but shows highly increased conductivity of 4.50 × 10(-3) S/m under sunlight. Photovoltaic devices based on this kind of photoactive cathode interlayer exhibit significantly improved device performance, which is rather insensitive to the thickness of the cathode interlayer over a broad range. Moreover, a power conversion efficiency as high as 10.5% was obtained by incorporation of our photoconductive cathode interlayer with the PTB7-Th:PC71BM active layer, which is one of the best results for single-junction polymer solar cells.

In Situ Electrochemical Synthesis and Deposition of Discotic Hexa-peri-hexabenzocoronene Molecules on Electrodes: Self-Assembled Structure, Redox Properties, and Application for Supercapacitor.

Discotic hexa-peri-hexabenzocoronene (HBC) molecules are synthesized by electrochemical cyclodehydrogenation reaction and in situ self-assembled to π-electronic, discrete nanofibular objects with an average diameter about 70 nm, which are deposited directly onto the electrode. The nanofibers consist of columnar arrays of the π-stacked HBC molecules and the intercolumnar distance is determined to be 1.19 nm by X-ray diffraction, which corresponds well to the distance of 1.1 nm observed by high-resolution transmitting electron microscopy. The diameter of the molecular columns matches the size of the discotic HBC molecule indicating face-to-face π-stacking of HBC units in the column. The HBC nanofibers on electrode are redox active, and the nanosized columnar structures provide a huge surface area, which is a great benefit for the charging/discharging process, delivering excellent capacitance of 155 F g(-1) . The described electrochemical deposition method shows great advantage for self-assembling the family of insoluble and structurally designable graphene-like nano materials, which constitutes an important step toward molecular electronics.

Multicolored-fluorescence switching of ICT-type organic solids with clear color difference: mechanically controlled excited state.

A donor-acceptor-type fluorophore containing a twisted diphenylacrylonitrile and triphenylamine has been developed by using the Suzuki reaction. The system indicates typical intramolecular charge-transfer properties. Upon mechanical grinding or hydrostatic pressure, the fluorophore reveals a multicolored fluorescence switching. Interestingly, a fluorescence color transition from green to red was clearly observed, and the change of photoluminescent (PL) wavelength gets close to 111 nm. The mechanisms of high-contrast mechanochromic behavior are fully investigated by techniques including powder XRD, PL lifetime, high-pressure PL lifetime, and Raman spectra analysis. The tremendous PL wavelength shift is attributed to gradual transition of excited states from the local excited state to the charge-transfer state.

Cyano-substituted oligo(p-phenylene vinylene) single-crystal with balanced hole and electron injection and transport for ambipolar field-effect transistors.

High and balanced hole and electron mobilities were achieved in OFETs based on the high photoluminescence of a 1,4-bis(2-cyano-2-phenylethenyl)benzene single-crystal with symmetric electrodes. For electron and hole, the operation voltage in the OFETs based on symmetric gold electrodes was 30 and -20 V, respectively. The accumulation threshold voltage is low enough for the OFETs to operate in an ambipolar model with the source/drain voltage (Vds) around 50 V despite the high injection barrier. The highest electron and hole mobility was 0.745 cm(2) V(-1) s(-1) and 0.239 cm(2) V(-1) s(-1), and the current density reached 90.7 and 27.4 A cm(-2), respectively with an assumed 10 nm accumulation layer. The high mobility comes from the strong π-π interactions. In addition, the highly ordered hydrogen bonding matrix may create an efficient route to pump the charge to the inner layer which can improve the injection ability.

Biphasic self-assembly pathways and size-dependent photophysical properties of perylene bisimide dye aggregates.

The concentration-dependent absorption and temperature-dependent fluorescence of the perylene bisimide dye PBI 1 in methylcyclohexane point to a biphasic aggregation behavior. At intermediate concentrations and temperatures, respectively, a dimer with low fluorescence yield dominates, which cannot be extended to longer aggregates. Those are formed at high concentrations and low temperatures, respectively, via a second, energetically unfavorable dimer species that acts as a nucleus. A corresponding aggregation model reproduces accurately the concentration dependence and allows extracting the equilibrium constants and spectra of the distinct species. The differences in the photophysical properties indicate H-type excitonic coupling for the favored dimer and J-type characteristics for the extended aggregates which could be related to structural models based on DFT calculations. The energetics can be understood by considering hydrogen-bonding and π-π-stacking interactions.