n-Type Fullerene-Carbon Dots: Synthesis and Electrochemical and Photophysical Properties.

The covalent incorporation of C60 and C70 derivatives of the well-known n-type organic semiconductor PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) onto carbon dots (CD) is described. Morphological and structural characterization reveal combined features of both pristine starting materials (CD and PCBM). Electrochemical investigations evidenced the existence of additional reduction processes to that of CD or PCBM precursors, showing rich electron-acceptor capabilities, with multistep processes in an affordable and narrow electrochemical window (ca. 1.5 V). Electronic communication in the obtained nanoconjugated species were derived from steady-state absorption and emission spectroscopies, which showed bathochromically shifted absorptions and emissions well entering the red region. Finally, the lower fluorescence quantum yield of CD-PCBM nanoconjugates, compared with CD, and the fast decay of the observed emission of CD, support the existence of an electronic communication between both CD and PCBM units in the excited state.

Insights into the origins of inverted circular dichroism in thin films of a chiral side chain polyfluorene.

We synthesized a fluorene-bithiophene co-polymer with chiral side chains (cPFT2) and investigated its chiroptical properties via synchotronradiation circular dichroism. We observed that thin films of the polymer display an intense circular dichroism (CD) upon annealing, which is of opposite handedness to the CD reported for similar polyfluorenes bearing the same enantiomeric chiral side chain. We then contrast the properties of this polymer with chiral side chain fluorene homopolymer (cPF) and observe large differences in their thin film morphology. Using photoluminescence spectroscopy, we uncover evidence of polymer chain bending in cPFT2, which is further supported by theoretical calculations, and propose an explanation for the observed inverted optical activity.

Critical role of H-aggregation for high-efficiency photoinduced charge generation in pristine pentamethine cyanine salts.

The mechanism of photoinduced symmetry-breaking charge separation in solid cyanine salts at the base of organic photovoltaic and optoelectronic devices is still debated. Here, we employ femtosecond transient absorption spectroscopy (TAS) to monitor the charge transfer processes occurring in thin films of pristine pentamethine cyanine (Cy5). Oxidized dye species are observed in Cy5-hexafluorophosphate salts upon photoexcitation, resulting from electron transfer from monomer excited states to H-aggregates. The charge separation proceeds with a quantum yield of 86%, providing the first direct proof of high efficiency intrinsic charge generation in organic salt semiconductors. The impact of the size of weakly coordinating anions on charge separation and transport is studied using TAS alongside electroabsorption spectroscopy and time-of-flight techniques. The degree of H-aggregation decreases with increasing anion size, resulting in reduced charge transfer. However, there is little change in carrier mobility, as despite the interchromophore distance increasing, the decrease in energetic disorder helps to alleviate the trapping of charges by H-aggregates.

Enhancing Circularly Polarized Electroluminescence through Energy Transfer within a Chiral Polymer Host.

Organic light-emitting diodes (OLEDs) that are able to emit high levels of circularly polarized (CP) light hold significant promise in numerous future technologies. Such devices require chiral emissive materials to enable CP electroluminescence. However, the vast majority of current OLED emitter classes, including the state-of-the-art triplet-harvesting Thermally Activated Delayed Fluorescence (TADF) materials, produce very low levels of CP electroluminescence. Here we showcase a host-guest strategy that allows for energy transfer between a chiral polymer host and a representative chiral TADF emitter. Such a mechanism results in large amplification of the circular polarization of the emitter. As such, this study presents a promising avenue to further boost the performance of CP-OLED devices, enabling their further development and eventual commercialization. This article is protected by copyright. All rights reserved.

Bulk Heterojunction Organic Semiconductor Photoanodes: Tuning Energy Levels to Optimize Electron Injection.

The use of a bulk heterojunction of organic semiconductors to drive photoelectrochemical water splitting is an emerging trend; however, the optimum energy levels of the donor and acceptor have not been established for photoanode operation with respect to electrolyte pH. Herein, we prepare a set of donor polymers and non-fullerene acceptors with varying energy levels to probe the effect of photogenerated electron injection into a SnO2-based substrate under sacrificial photo-oxidation conditions. Photocurrent density (for sacrificial oxidation) up to 4.1 mA cm-2 was observed at 1.23 V vs reversible hydrogen electrode in optimized photoanodes. Moreover, we establish that a lower-lying donor polymer leads to improved performance due to both improved exciton separation and better charge collection. Similarly, lower-lying acceptors also give photoanodes with higher photocurrent density but with a later photocurrent onset potential and a narrower range of pH for good operation due to the Nernstian behavior of the SnO2, which leads to a smaller driving force for electron injection at high pH.