Perylene diimide (PDI) is one of the most studied functional dyes due to their structural versatility and fine tuning of the materials properties. Core substituted PDIs are prominent n-type semiconductor materials that could be used as non-fullerene acceptors in organic photovoltaics. Herein, we develop versatile organic building blocks based on PDI by decorating the PDI core with quinoline groups. Styryl and hydroxy phenyl mono and difunctionalized molecules were prepared using mono-nitro and dibromo bay substituted PDIs by Suzuki coupling with the respective boronic acid derivatives. A novel methodology using nitro-PDI under Suzuki coupling conditions as an electrophile partner was successfully tested. Furthermore, the PDI derivatives were used for the synthesis of soluble, electron accepting small molecules combining PDI with weak electron withdrawing quinoline derivatives. The new molecules presented wide absorbance in the visible spectrum from 450 to almost 700 nm while their LUMO levels and their energy levels are in the range of −3.8 to −4.2 eV.
Conjugation-break flexible spacers in-between πconjugated segments were utilized herein toward processable perylene diimide (PDI)-based polymers. Aromatic−aliphatic PDIbased polymers were developed via the two-phase polyetherification of a phenol-difunctional PDI monomer and aliphatic dibromides. These polyethers showed excellent solubility and filmforming ability and deep lowest unoccupied molecular orbital (LUMO) levels (−4.0 to −3.85 eV), indicating the preservation of good electron-accepting character or characteristics, despite the non-conjugated segments. Their thermodynamic properties, local dynamics, and ionic conductivity demonstrate the suppression of PDI's inherent tendency for aggregation and crystallization, suggesting PDI-polyethers as versatile candidates for organic electronic applications. Their dynamics investigation using dielectric spectroscopy revealed weak dipole moments arising from the distortion of the planar perylene cores. Blends of the PDI-polyethers (as electron acceptors) with P3HT (as a potential electron donor component) showed UV−vis absorbances from 350 to 650 nm and a tendency of the PDI-polyethers to intertwine with rr-P3HT and restrain its high crystallization tendency.
Oligomers of the low-band-gap PCDTBT polymer, based on either 3,6 or 2,7 carbazole units, were modified with vinyl ω-chain end functionalities. The vinyl-functionalized oligomers were used as comonomers in free radical polymerizations with quinoline-based monomers such as 6-vinylphenyl-(2-pyridinyl)-4-phenyl-quinoline (vinyl-QPy), and 6-vinylphenyl-(2-perfluorophenyl)-4-phenyl quinoline (vinyl-5FQ). The co-polymeric materials bearing the vinyl-QPy moiety were developed as potential compatibilizers in polymer electron donor–fullerene acceptor blends for non-covalent interactions with the fullerene part. The co-polymeric materials bearing the vinyl-5FQ moiety were developed for the covalent attachment of carbon nanostructures; specifically, PC61BM. Both copolymers and hybrids, after thorough purification, were characterized in terms of their spectroscopic and optical properties as well as their ability to form nanophased separated films as such, or as additives at various percentages into PCDTBT: PC71BM blends.
For the first time in dye-sensitized solar cell (DSSC) technology, a di-carbazole-based dye was synthesized and evaluated for its usage as a potential sensitizer for the development of wavelength selective semi-transparent DSSCs for greenhouses-oriented applications. The dye was designed to demonstrate a blue light absorption, allowing a high transmittance in the red region of the visible light, even after its adsorption on the anode semiconductor, which is the most important one for the photosynthetic action of the plants. The application of the new dye to DSSCs was examined using either a high-performance iodide-based electrolyte or a highly transparent iodine-free electrolyte to determine a good balance between electric power generation and device transparency. The spectral engineered DSSCs demonstrated quite promising characteristics, providing a high external quantum efficiency (higher than 70%) in the whole blue–green region of the visible light, while allowing high transparency (up to 55%) in the red region, where the second peak in the absorbance spectrum of chlorophyll is located. Finally, the derived results were discussed under the consideration of important metrics for this niche application, including the transparency of the solar cells in the region of photosynthetic active radiation and the attained crop growth factor. The present work constitutes one of the few comprehensive studies carried out up to now in the direction of the development of 3rd generation “agrivoltaics” for their possible integration as cladding materials in energy-autonomous greenhouses.
A route toward processable n-type terpolymers is presented herein based on the random donor–acceptor–donor–acceptor (D–A1)-(D–A2) molecular configuration. Carbazole is utilized as the electron donating unit (D) combined with perylene diimide (PDI) as the first electron acceptor (A1) and either one of two different benzothiadiazole (BTZ) derivatives (di-thienyl substituted-BTZ and di-3,4-ethylenedioxythienyl substituted-BTZ) as the second electron accepting unit (A2). Increasing the content of the PDI co-monomer resulted in terpolymers of higher molecular weights, enhanced solubility, and stronger n-type character. The physicochemical properties of the random PDI-Cz-BTZ derivatives are fine-tuned based on the feed ratio of the co-monomers. Photodiode devices were demonstrated, having photoactive layers composed of the rich in PDI terpolymer, namely, P4 having a 75% PDI content, and the PCE10 electron donor, under various ratios. For a range of P4 blend compositions, UV–Vis, is spectroscopy confirmed the strong absorption of the blend films across the 350–800 nm spectral region, and AFM imaging verified their low surface roughness. The study of the electro-optical device properties identified the 1:2 blending ratio as the optimum PCE10:P4 combination for maximum charge photogeneration efficiency. Despite the relatively deep LUMO energy of the n-type P4 terpolymer (E LUMO = −4.04 eV), trap-induced charge recombination losses were found to limit the PCE10:P4 photodiode performance. Unipolar devices of the P4-alone exhibited hole and electron mobility values of 2.2 × 10–4 and 6.3 × 10–5 cm2 V–1 s–1, respectively.
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