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Abstract:
Development and step-by-step characterizations of a novel cationic thiophene based copolymer (P1buP), including ionic phosphonium salt and dye-tetraphenylporphyrin (TPP) moiety in side chains, with an iconic property of solubility in a wide range of polar solvents is reported. Synthesized by using simple, low-cost, and straightforward procedures, the material is used to fabricate completely halogen-free (i.e., from ethanol) ternary organic solar cells (OSCs), in the presence of an alcohol-soluble ionic 3,4-dialkoxythiophene based homopolymer (P2buP) and a serinol-fullerene derivative (C60-Ser). Indeed, thanks to co-sensitization techniques, where multiple dyes harvest different parts of the solar spectrum, the power conversion efficiency of the best final device dramatically increases up to nearly 5.0%, as the light absorption is usually optimized. Additionally, since the use of a cathode interlayer in OSCs also plays a pivotal role in electron extraction and device stability, a possible application of the ionic TPP material as the interfacial layer is also investigated. Furthermore, to improve and optimize the best performing device, a successful post-metalation with Zn of the porphyrin core is carried out, and a ternary OSC (P1buP:P2buP:C60-Ser = 0.33:0.67:1 w/w) is fabricated, resulting in a photoconversion efficiency (PCE) of ∼6.0%.

Keywords:
Ionic dye-tetraphenylporphyrin, Co-sensitization, Ternary OSCs, Cathode interlayers, Halogen-free deposition

Abstract:
In this study, we introduce a novel family of symmetrical thiophene-based small molecules with a Donor–Acceptor–Donor structure. These compounds feature three different acceptor units: benzo[c][1,2,5]thiadiazole (Bz), thieno[3,4-b]pyrazine (Pz), and thieno[1,2,5]thiadiazole (Tz), coupled with electron donor units based on a carbazole-thiophene derivative. Using Density Functional Theory (DFT), we investigate how the molecular geometry and strength of the central acceptor unit impact the redox and spectroscopic properties. Notably, the incorporation of Pz and Tz moieties induces a significant redshift in the absorption and emission spectra, which extend into the near-infrared (NIR) region, simultaneously reducing their energy gaps (~1.4-1.6 eV). This shift is attributed to the increased coplanarity of the oligomeric inner core, both in the ground (S0) and excited (S1) states, due to the enhanced quinoidal character as supported by bond-length alternation (BLA) analysis. These structural changes promote better π-electron delocalization and facilitate photoinduced charge transfer processes in optoelectronic devices. Notably, we show that Pz- and Tz-containing molecules exhibit NIR electrochromic behavior and present ambivalent character in bulk heterojunction (BHJ) solar cells. Finally, theoretical calculations suggest that these molecules could serve as effective two-photon absorption (2PA) probes, further expanding their potential in optoelectronic applications.

Abstract:
Three new ionic polythiophene derivatives, soluble in polar solvents, are synthesized with good yields using simple, low-cost, and straightforward procedures. They are investigated as interfacial cationic conjugated
polyelectrolyte (CPE) layers for halogen-free bulk heterojunction polymeric solar cells, based on a water-soluble electron-donor polymer
(poly[3-(6-diethanolaminohexyl)thiophene]) and a water-soluble electron-acceptor fullerene derivative (malonodiserinolamide fullerene). The simple insertion of the CPE interlayer between the active layer and the aluminum cathode dramatically increases the power conversion efficiency of the final device up to nearly 5%, resulting from a decrease of the electrode work function, improved electron extraction, and optimization of the morphology of the layers. The obtained results demonstrate that the incorporation of CPE layer is a powerful and convenient methodology for the
development of highly efficient and eco-friendly processable polymeric solar cells.

Keywords:
conjugated polyelectrolyte,electron transport layers,polythiophene

Abstract:
Four new conjugated polymers alternating benzothiadiazole units and thiophene moieties functionalized with ionic phosphonium or sulfonic acid salts in the side chains were synthesized by a postfunctionalization approach of polymeric precursors. The introduction of ionic groups makes the conjugated polymers soluble in water and/or polar solvents, allowing for the fabrication of bulk heterojunction (BHJ) solar cells using environmentally friendly conditions. All polymers were fully characterized by spectroscopic, thermal, electrochemical, X-ray diffraction, scanning electron, and atomic force techniques. BHJ solar cells were obtained from halogen-free solvents (i.e., ethanol and/or anisole) by blending the synthesized ionic push–pull polymers with a serinol-fullerene derivative or an ionic homopolymer acting as electron-acceptor (EA) or electron-donor (ED) counterparts, respectively. The device with the highest optical density and the smoothest surface of the active layer was the best-performing, showing a 4.76% photoconversion efficiency.

Keywords:
donor–acceptor systems, bifunctional materials, phosphonium salts, eco-friendly BHJ solar cells, anisole

Abstract:
Here is reported an expedient synthesis implementing enabling technologies of a family of thiophene-based heptamers alternating electron donor (D) and acceptor (A) units in a D–A′–D–A–D–A′–D sequence. The nature of the peripheral A groups (benzothiadiazole vs. thienopyrrole-dione vs. thiophene-S,S-dioxide) and the strength of the donor units (alkyl vs. thioalkyl substituted thiophene ring) have been varied to finely tune the chemical-physical properties of the D–A oligomers, to affect the packing arrangement in the solid-state as well as to enhance the photovoltaic performances. The optoelectronic properties of all compounds have been studied by means of optical spectroscopy, electrochemistry, and density functional theory calculations. Electrochemical measurements and Kelvin probe force microscopy (KPFM) predicted a bifunctional behaviour for these oligomers, suggesting the possibility of using them as donor materials when blended with PCBM, and as acceptor materials when coupled with P3HT. Investigation of their photovoltaic properties confirmed this unusual characteristic, and it is shown that the performance can be tuned by the different substitution pattern. Furthermore, thanks to their ambivalent character, binary non-fullerene small-molecule organic solar cells with negligible values of HOMO and LUMO offsets were also fabricated, resulting in PCEs ranging between 2.54–3.96%.

Abstract:
A new side-chain C60-fullerene functionalized thiophene copolymer bearing tributylphosphine-substituted hexylic lateral groups was successfully synthesized by means of a fast and effective post-polymerization reaction on a regioregular ω-alkylbrominated polymeric precursor. The growth of the polymeric intermediate was followed by NMR spectrometry in order to determine the most convenient reaction time. The obtained copolymer was soluble in water and polar solvents and was used as a photoactive layer in single-material organic photovoltaic (OPV) solar cells. The copolymer photovoltaic efficiency was compared with that of an OPV cell containing a water-soluble polythiophenic homopolymer, functionalized with the same tributylphosphine-substituted hexylic side chains, in a blend with a water-soluble C60-fullerene derivative. The use of a water-soluble double-cable copolymer made it possible to enhance the control on the nanomorphology of the active blend, thus reducing phase-segregation phenomena, as well as the macroscale separation between the electron acceptor and donor components. Indeed, the power conversion efficiency of OPV cells based on a single material was higher than that obtained with the classical architecture, involving the presence of two distinct ED and EA materials (PCE: 3.11% vs. 2.29%, respectively). Moreover, the synthetic procedure adopted to obtain single material-based cells is more straightforward and easier than that used for the preparation of the homopolymer-based BHJ solar cell, thus making it possible to completely avoid the long synthetic pathway which is required to prepare water-soluble fullerene derivatives.

Keywords:
water-soluble polymers, double-cable copolymers, polythiophenes, GRIM polymerization, tributylphosphine, water-soluble fullerenes, OPVs

Abstract:
Multifunctional nanomaterials with the ability torespond to near-infrared (NIR) light stimulation are vital for thedevelopment of highly efficient biomedical nanoplatforms with apolytherapeutic approach. Inspired by the mesoglea structure ofjellyfish bells, a biomimetic multifunctional nanostructured pillowwith fast photothermal responsiveness for NIR light-controlled on-demand drug delivery is developed. We fabricate a nanoplatformwith several hierarchical levels designed to generate a series ofcontrolled, rapid, and reversible cascade-like structural changesupon NIR light irradiation. The mechanical contraction of thenanostructured platform, resulting from the increase of temper-ature to 42°C due to plasmonic hydrogel−light interaction, causesa rapid expulsion of water from the inner structure, passing through an electrospun membrane anchored onto the hydrogel core. Themutual effects of the rise in temperature and waterflow stimulate the release of molecules from the nanofibers. To expand thepotential applications of the biomimetic platform, the photothermal responsiveness to reach the typical temperature level forperforming photothermal therapy (PTT) is designed. The on-demand drug model penetration into pig tissue demonstrates theefficiency of the nanostructured platform in the rapid and controlled release of molecules, while the high biocompatibility confirmsthe pillow potential for biomedical applications based on the NIR light-driven multitherapy strategy.

Keywords:
bioinspired materials, NIR-light responsive nanomaterials, multifunctional platforms, electrospun nanofibers, plasmonic hydrogel, photothermal-based polytherapy, on-demand drug delivery

Abstract:
Side‐chain C60‐fullerene functionalized alkylthiophene copolymers with different regioregularity and fullerene content are successfully synthesized using a simple and straightforward post‐polymerization functionalization procedure based on a Grignard coupling reaction. The products are employed as single materials in photoactive layers of organic photovoltaic solar cells. The use of double‐cable polymers allows an enhanced control on the nanomorphology of the active blend, reducing the phase‐segregation phenomena as well as the macroscale separation between the electron acceptor and donor components. With the insertion of a thin layer of gold nanoparticles between buffer and active layer of the cells, a conversion efficiency of 5.68% is obtained. Moreover, an increased stability over time is achieved when the copolymers are photocrosslinked immediately after the annealing procedure, leading to acceptable efficiencies even after 80 h of accelerated ageing, a key feature for widespread applicability of the prepared devices.

Keywords:
conjugated polymers, fullerenes, functionalization of polymers, metathesis

Abstract:
Two water-soluble regioregular poly(3-alkylthiophene)s, incorporating aminic groups at the end of the side chains, have been synthesized using a post-polymerization functionalization procedure on a ω-bromine substituted polyalkylthiophene. The high solubility of the obtained polymers in water allowed for the preparation of “green” bulk heterojunction solar cells which reached a power conversion efficiency of 4.85% when PC61BM was used as electron-acceptor material. Improved optical absorption and photocurrent have been obtained by interposing a layer of Ag nanoparticles between the buffer and the photoactive layer, leading to a final power conversion efficiency of 5.51%.

Keywords:
Water-soluble polythiophene, Bulk heterojunction solar cell, Organic photovoltaic

Abstract:
Water-soluble regioregular poly{3-[(6-sodium sulfonate)hexyl]thiophene} (PT6S) and poly{3-[(6-trimethylammoniumbromide)hexyl]thiophene} (PT6N) have been synthesized and employed both as photoactive layers for the assembling of “green” bulk-heterojunction organic solar cells and as charge-collection layers in a cell with “classic” architecture. While the photovoltaic performances obtained with the two aforementioned polymers were lower than the reference cell, their latter use allowed to notably increase the inherent J-V properties, leading to a considerable enhancement in the overall photovoltaic output. The power conversion efficiency of the optimized multilayer BHJ solar cell reached 4.78%, revealing a higher efficiency than the reference cell (3.63%).

Keywords:
Water-soluble polymer, Polythiophene derivative, Bulk heterojunction, Organic photovoltaic, Interfacial layer

Abstract:
A novel thiophenic tetramer containing a cinnamate group in the side chain with a functionalization degree of 50% is reported. The tetramer was obtained by means of a simple and straightforward procedure involving the functionalization of a p-methoxyphenoxy substituted thiophenic precursor, which led to a soluble product with a good yield. The oligomer was fully characterized from a structural and chemical point of view and employed for the fabrication of small molecule organic solar cells exploiting the bulk heterojunction (BHJ) architecture. The presence of an UV-light sensitive group in the tetramer allowed the photocrosslinking of tetramer/PCBM blends, giving high values of photocurrent and conversion efficiency for the exposed samples. Moreover, the UV-treated devices showed improved stability, even upon heating for three days at 130 °C, thus confirming that photocrosslinking can strongly reduce phase segregation under severe operational conditions.

Keywords:
electronic materials, polymers, fullerenes, nanostructures, electrical characterization, semiconductors