Elucidating Singlet-Fission-Born Multiexciton Dynamics via Molecular Engineering: A Dilution Principle Extended to Quintet Triplet Pair.

Multiexciton in singlet exciton fission represents a critical quantum state with significant implications for both solar cell applications and quantum information science. Two distinct fields of interest explore contrasting phenomena associated with the geminate triplet pair: one focusing on the persistence of long-lived correlation and the other emphasizing efficient decorrelation. Despite the pivotal nature of multiexciton processes, a comprehensive understanding of their dependence on the structural and spin properties of materials is currently lacking in experimental realizations. To address this gap in knowledge, molecular engineering was employed to modify the TIPS-tetracene structures, enabling an investigation of the structure-property relationships in spin-related multiexciton processes. In lieu of the time-resolved electron paramagnetic resonance technique, two time-resolved magneto-optical spectroscopies were implemented for quantitative analysis of spin-dependent multiexciton dynamics. The utilization of absorption and fluorescence signals as complementary optical readouts, in the presence of a magnetic field, provided crucial insights into geminate triplet pair dynamics. These insights encompassed the duration of multiexciton correlation and the involvement of the spin state in multiexciton decorrelation. Furthermore, simulations based on our kinetic models suggested a role for quintet dilution in multiexciton dynamics, surpassing the singlet dilution principle established by the Merrifield model. The integration of intricate model structures and time-resolved magneto-optical spectroscopies served to explicitly elucidate the interplay between structural and spin properties in multiexciton processes. This comprehensive approach not only contributes to the fundamental understanding of these processes but also aligns with and reinforces previous experimental studies of solid states and theoretical assessments.

Supramolecular Reconstruction of Self-Assembling Photosensitizers for Enhanced Photocatalytic Hydrogen Evolution.

Natural photosynthetic systems require spatiotemporal organization to optimize photosensitized reactions and maintain overall efficiency, involving the hierarchical self-assembly of photosynthetic components and their stabilization through synergistic interactions. However, replicating this level of organization is challenging due to the difficulty in efficiently communicating supramolecular nano-assemblies with nanoparticles or biological architectures, owing to their dynamic instability. Herein, we demonstrate that the supramolecular reconstruction of self-assembled amphiphilic rhodamine B nanospheres (RN) through treatment with metal-phenolic coordination complexes results in the formation of a stable hybrid structure. This reconstructed structure enhances electron transfer efficiency, leading to improved photocatalytic performance. Due to the photoluminescence quenching property of RN and its electronic synergy with tannic acid (T) and zirconium (Z), the supramolecular complexes of hybrid nanospheres (RNTxZy) with Pt nanoparticles or a biological workhorse, Shewanella oneidensis MR-1, showed marked improvement in photocatalytic hydrogen production. The supramolecular hybrid particles with a metal-phenolic coordination layer showed 5.6- and 4.0-fold increases, respectively, in the productivities of hydrogen evolution catalyzed by Pt (Pt/RNTxZy) and MR-1 (M/RNTxZy), respectively. These results highlight the potential for further advancements in the structural and photochemical control of supramolecular nanomaterials for energy harvesting and bio-hybrid systems.

Synergistic Contribution of Oligo(ethylene glycol) and Fluorine Substitution of Conjugated Polymer Photocatalysts toward Solar Driven Sacrificial Hydrogen Evolution.

To separately explore the importance of hydrophilicity and backbone planarity of polymer photocatalyst, a series of benzothiadiazole-based donor-acceptor alternating copolymers incorporating alkoxy, linear oligo(ethylene glycol) (OEG) side chain, and backbone fluorine substituents is presented. The OEG side chains in the polymer backbone increase the surface energy of the polymer nanoparticles, thereby improving the interaction with water and facilitating electron transfer to water. Moreover, the OEG-attached copolymers exhibit enhanced intermolecular packing compared to polymers with alkoxy side chains, which is possibly attributed to the self-assembly properties of the side chains. Fluorine substituents on the polymer backbone produce highly ordered lamellar stacks with distinct π-π stacking features; subsequently, the long-lived polarons toward hydrogen evolution are observed by transient absorption spectroscopy. In addition, a new nanoparticle synthesis strategy using a methanol/water mixed solvent is first adopted, thereby avoiding the screening effect of surfactants between the nanoparticles and water. Finally, hydrogen evolution rate of 26 000 µmol g-1  h-1 is obtained for the copolymer incorporated with both OEG side chains and fluorine substituents under visible-light irradiation (λ > 420 nm). This study demonstrates how the glycol side chain strategy can be further optimized for polymer photocatalysts by controlling the backbone planarity.

Correlating Charge-Transfer State Lifetimes with Material Energetics in Polymer:Non-Fullerene Acceptor Organic Solar Cells.

Minimizing the energy offset between the lowest exciton and charge-transfer (CT) states is a widely employed strategy to suppress the energy loss (Eg/q - VOC) in polymer:non-fullerene acceptor (NFA) organic solar cells (OSCs). In this work, transient absorption spectroscopy is employed to determine CT state lifetimes in a series of low energy loss polymer:NFA blends. The CT state lifetime is observed to show an inverse energy gap law dependence and decreases as the energy loss is reduced. This behavior is assigned to increased mixing/hybridization between these CT states and shorter-lived singlet excitons of the lower gap component as the energy offset ΔECT-S1 is reduced. This study highlights how achieving longer exciton and CT state lifetimes has the potential for further enhancement of OSC efficiencies.

Enhanced photocatalytic hydrogen evolution from organic semiconductor heterojunction nanoparticles.

Photocatalysts formed from a single organic semiconductor typically suffer from inefficient intrinsic charge generation, which leads to low photocatalytic activities. We demonstrate that incorporating a heterojunction between a donor polymer (PTB7-Th) and non-fullerene acceptor (EH-IDTBR) in organic nanoparticles (NPs) can result in hydrogen evolution photocatalysts with greatly enhanced photocatalytic activity. Control of the nanomorphology of these NPs was achieved by varying the stabilizing surfactant employed during NP fabrication, converting it from a core-shell structure to an intermixed donor/acceptor blend and increasing H2 evolution by an order of magnitude. The resulting photocatalysts display an unprecedentedly high H2 evolution rate of over 60,000 µmol h-1 g-1 under 350 to 800 nm illumination, and external quantum efficiencies over 6% in the region of maximum solar photon flux.

Tracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution.

Semiconducting polymers are versatile materials for solar energy conversion and have gained popularity as photocatalysts for sunlight-driven hydrogen production. Organic polymers often contain residual metal impurities such as palladium (Pd) clusters that are formed during the polymerization reaction, and there is increasing evidence for a catalytic role of such metal clusters in polymer photocatalysts. Using transient and operando optical spectroscopy on nanoparticles of F8BT, P3HT, and the dibenzo[b,d]thiophene sulfone homopolymer P10, we demonstrate how differences in the time scale of electron transfer to Pd clusters translate into hydrogen evolution activity optima at different residual Pd concentrations. For F8BT nanoparticles with common Pd concentrations of >1000 ppm (>0.1 wt %), we find that residual Pd clusters quench photogenerated excitons via energy and electron transfer on the femto-nanosecond time scale, thus outcompeting reductive quenching. We spectroscopically identify reduced Pd clusters in our F8BT nanoparticles from the microsecond time scale onward and show that the predominant location of long-lived electrons gradually shifts to the F8BT polymer when the Pd content is lowered. While a low yield of long-lived electrons limits the hydrogen evolution activity of F8BT, P10 exhibits a substantially higher hydrogen evolution activity, which we demonstrate results from higher yields of long-lived electrons due to more efficient reductive quenching. Surprisingly, and despite the higher performance of P10, long-lived electrons reside on the P10 polymer rather than on the Pd clusters in P10 particles, even at very high Pd concentrations of 27000 ppm (2.7 wt %). In contrast, long-lived electrons in F8BT already reside on Pd clusters before the typical time scale of hydrogen evolution. This comparison shows that P10 exhibits efficient reductive quenching but slow electron transfer to residual Pd clusters, whereas the opposite is the case for F8BT. These findings suggest that the development of even more efficient polymer photocatalysts must target materials that combine both rapid reductive quenching and rapid charge transfer to a metal-based cocatalyst.

Morphology Driven by Molecular Structure of Thiazole-Based Polymers for Use in Field-Effect Transistors and Solar Cells.

The effects of the molecular structure of thiazole-based polymers on the active layer morphologies and performances of electronic and photovoltaic devices were studied. Thus, thiazole-based conjugated polymers with a novel thiazole-vinylene-thiazole (TzVTz) structure were designed and synthesized. The TzVTz structure was introduced to extend the π conjugation and coplanarity of the polymer chains. By combining alkylthienyl-substituted benzo[1,2-b:4,5-b']dithiophene (BDT) or dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene (DTBDT) electron-donating units and a TzVTz electron-accepting unit, enhanced intermolecular interactions and charge transport were obtained in the novel polymers BDT-TzVTz and DTBDT-TzVTz. With a view to using the polymers in transistor and photovoltaic applications, the molecular self-assembly in and their nanoscale morphologies of the active layers were controlled by thermal annealing to enhance the molecular packing and by introducing a diphenyl ether solvent additive to improve the miscibility between polymer donors and [6,6]phenyl-C71-butyric acid methyl ester (PC71 BM) acceptors, respectively. The morphological characterization of the photoactive layers showed that a higher degree of π-electron delocalization and more favorable molecular packing in DTBDT-TzVTz compared with in BDT-TzVTz leads to distinctly higher performances in transistor and photovoltaic devices. The superior performance of a photovoltaic device incorporating DTBDT-TzVTz was achieved through the superior miscibility of DTBDT-TzVTz with PC71 BM and the improved crystallinity of DTBDT-TzVTz in the nanofibrillar structure.

Acene-Modified Small-Molecule Donors for Organic Photovoltaics.

A series of acene-modified small molecules have been designed and synthesized, and their photovoltaic characteristics were studied by using the small molecules in organic photovoltaics (OPVs). Different cores were introduced to modulate the conjugation lengths of the small molecules and the bulk heterojunction (BHJ) morphologies. Three small-molecule donors were prepared, namely Ph-TTR, Na-TTR, and An-TTR, which have phenyl, naphthalene, and anthracene moieties, respectively, as conjugated cores. These donors were synthesized in a few steps and exhibited favorable BHJ morphologies, thereby giving promising power conversion efficiencies (PCEs). The donors showed excellent miscibility with the acceptor PC71 BM, and the use of the additive 1,8-diiodooctane (DIO) led to a remarkable increase in crystallinity, thereby increasing the PCEs of their OPVs. Of the three donors, Na-TTR showed the most efficient charge carrier generation and favorable molecular packing structures; hence, of the three types of devices tested, the Na-TTR:PC71 BM devices exhibited the highest PCE, specifically 6.27 %, without pre- or post-treatments. The promising PCEs achieved from these easily synthesized acene-modified small molecules suggested that acene-modified small molecules can be useful materials in OPVs.

The binding energy and dynamics of charge-transfer states in organic photovoltaics with low driving force for charge separation.

Recent progress in organic photovoltaics (OPVs) has been enabled by optimization of the energetic driving force for charge separation, and thus maximization of open-circuit voltage, using non-fullerene acceptor (NFA) materials. In spite of this, the carrier dynamics and relative energies of the key states controlling the photophysics of these systems are still under debate. Herein, we report an in-depth ultrafast spectroscopic study of a representative OPV system based on a polymer donor PffBT4T-2OD and a small-molecule NFA EH-IDTBR. Global analysis of the transient absorption data reveals efficient energy transfer between donor and acceptor molecules. The extracted kinetics suggest that slow (∼15 ps) generation of charge carriers is followed by significant geminate recombination. This contrasts with the "reference" PffBT4T-2OD:PC71BM system where bimolecular recombination dominates. Using temperature-dependent pump-push-photocurrent spectroscopy, we estimate the activation energy for the dissociation of bound charge-transfer states in PffBT4T-2OD:EH-IDTBR to be 100 ± 6 meV. We also observe an additional activation energy of 14 ± 7 meV, which we assign to the de-trapping of mobile carriers. This work provides a comprehensive picture of photophysics in a system representing new generation of OPV blends with a small driving force for charge separation.

Hirsutane-Type Sesquiterpenes with Inhibitory Activity of Microglial Nitric Oxide Production from the Red Alga-Derived Fungus Chondrostereum sp. NTOU4196.

The marine red alga Pterocladiella capillacea is an economic alga for the food industry in Taiwan, and its associated highly diversified fungi have not been investigated meticulously thus far. The EtOAc extract of the fermented broth of Chondrostereum sp. NTOU4196, a fungal strain isolated from P. capillacea, was found to exhibit significant nitric oxide (NO) production inhibitory activity in lipopolysaccharide-activated murine RAW 264.7 cells at a concentration of 100 µg/mL in the preliminary screening. Therefore, separation of the active principles from the fermented broths was performed, and that has led to the isolation of eight new 5,5,5-tricyclic hirsutane-type sesquiterpenes, namely, chondroterpenes A-H (1-8), together with seven known analogues. They were identified by analyses of spectroscopic data and comparison with literature values. Among the new isolates, chondroterpene A (1) exhibited more significant NO production inhibitory activity in murine BV-2 microglial cells, and of all the isolated compounds, hirsutanol A (9) exerted limited cytotoxic effects and the most potent inhibitory activity on NO production.

Angiogenesis Inhibitors and Anti-Inflammatory Agents from Phoma sp. NTOU4195.

Seven new polyketides, phomaketides A-E (1-5) and pseurotins A3 (6) and G (7), along with the known compounds FR-111142, pseurotins A, A1, A2, D, and F2, 14-norpseurotin A, α-carbonylcarbene, tyrosol, cyclo(-l-Pro-l-Leu), and cyclo(-l-Pro-l-Phe), were purified from the fermentation broth and mycelium of the endophytic fungal strain Phoma sp. NTOU4195 isolated from the marine red alga Pterocladiella capillacea. The structures were established through interpretation of spectroscopic data. The antiangiogenic and anti-inflammatory effects of 1-7 and related analogues were evaluated using human endothelial progenitor cells (EPCs) and lipopolysaccharide (LPS)-activated murine macrophage RAW264.7 cells, respectively. Of the compounds tested, compound 1 exhibited the most potent antiangiogenic activity by suppressing the tube formation of EPCs with an IC50 of 8.1 µM, and compound 3 showed the most selective inhibitory activity of LPS-induced NO production in RAW264.7 macrophages with an IC50 value of 8.8 µM.

Hydrophilic Photocrosslinkers as a Universal Solution to Endow Water Affinity to a Polymer Photocatalyst for an Enhanced Hydrogen Evolution Rate.

A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL-R) or ethylene glycol-based bridge chains (CL-TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365 nm. When employing the hydrophilic CL-TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5-fold compared to that obtained using non-crosslinked F8BT photocatalysts, whereas CL-R-based photocatalysts yield HER rates comparable to those of non-crosslinked counterparts. Photophysical analyses including time-resolved photoluminescence and transient absorption measurements reveal that adding CL-TEG accelerates exciton separation, forming long-lived charge carriers. Additionally, the in-depth study using molecular dynamics simulations elucidates the dual role of CL-TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high-permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts.

Enhancing the Efficiency and Stability of Tin-Lead Perovskite Solar Cells via Sodium Hydroxide Dedoping of PEDOT:PSS.

Tin-lead (Sn-Pb) perovskite solar cells (PSCs) have gained interest as candidates for the bottom cell of all-perovskite tandem solar cells due to their broad absorption of the solar spectrum. A notable challenge arises from the prevalent use of the hole transport layer, PEDOT:PSS, known for its inherently high doping level. This high doping level can lead to interfacial recombination, imposing a significant limitation on efficiency. Herein, NaOH is used to dedope PEDOT:PSS, with the aim of enhancing the efficiency of Sn-Pb PSCs. Secondary ion mass spectrometer profiles indicate that sodium ions diffuse into the perovskite layer, improving its crystallinity and enlarging its grains. Comprehensive evaluations, including photoluminescence and nanosecond transient absorption spectroscopy, confirm that dedoping significantly reduces interfacial recombination, resulting in an open-circuit voltage as high as 0.90 V. Additionally, dedoping PEDOT:PSS leads to increased shunt resistance and high fill factor up to 0.81. As a result of these improvements, the power conversion efficiency is enhanced from 19.7% to 22.6%. Utilizing NaOH to dedope PEDOT:PSS also transitions its nature from acidic to basic, enhancing stability and exhibiting less than a 7% power conversion efficiency loss after 1176 h of storage in N2 atmosphere.

Synthesis and transistor properties of asymmetric oligothiophenes: relationship between molecular structure and device performance.

A series of three thiophene-naphthalene-based asymmetric oligomers-5-decyl-2,2':5',2'':5'',2'''-quaterthiophene (DtT), 5-decyl-5''-(naphthalen-2-yl)-2,2':5',2''-terthiophene (D3TN), and 5-(4-decylphenyl)-5'-(naphthalen-2-yl)-2,2'-bithiophene (DP2TN)-was synthesized by Suzuki cross-coupling reactions. The long alkyl side chains improved both the solubility of the oligomers in solvents and their tendency to self-assemble. UV/Vis absorption measurements suggested that DtT, D3TN, and DP2TN form H-type aggregates with a face-to-face packing structure. In addition, the three oligomers were found to adopt vertically aligned crystalline structures in films deposited on substrates, as revealed by grazing-incidence wide-angle X-ray scattering. These oligomers were used as the active layers of p-type organic field-effect transistors, and the resulting devices showed field-effect mobilities of 3.3×10(-3)  cm(2) V(-1) s(-1) for DtT, 1.6×10(-2)  cm(2) V(-1) s(-1) for D3TN, and 3.7×10(-2)  cm(2) V(-1) s(-1) for DP2TN. The differences in transistor performances were attributed to the degree of π overlap and the morphological differences determined by the molecular structures.

Efficient Hole Transfer from a Twisted Perylenediimide Acceptor to a Conjugated Polymer in Organic Bulk-Heterojunction Solar Cells.

Non-fullerene acceptors have recently attracted tremendous interest due to their potential as alternatives to fullerene derivatives in bulk-heterojunction solar cells. Nevertheless, physical understanding of charge carrier generation and transfer mechanism that occurred at the interface between the non-fullerene molecule and donor polymer is still behind their enhanced photovoltaic performance. Here we report examples of a non-planar perylene dimer (TP) as an electron acceptor and achieve a power conversion efficiency of 6.29% in a fullerene-free solar cell. Photoluminescence (PL) measurements show high quenching efficiency driven by the excitons of both conjugated polymer and TP molecule, respectively, indicating efficient electron and hole transfer, which can support a highly intermixed phase of blends measured by atomic force microscopy (AFM) and grazing incident wide-angle X-ray diffraction (GIWAXS). Femtosecond transient absorption spectroscopy (fs-TAS) reveals that the fast exciton dissociation process from TP molecule to donor polymer contributes to additionally increasing current density, leading to stronger incident photon to current efficiency in the visible region.

Charge Carrier Dynamics in Non-Fullerene Acceptor-Based Organic Solar Cells: Investigating the Influence of Processing Additives Using Transient Absorption Spectroscopy.

In this study, we present a comprehensive investigation into the charge generation mechanism in bulk-heterojunction organic solar cells employing non-fullerene acceptors (NFAs) both with and without the presence of processing additives. While photovoltaic devices based on Y6 or BTP-eC9 have shown remarkable power conversion efficiencies, the underlying charge generation mechanism in polymer:NFA blends remains poorly understood. To shed light on this, we employ transient absorption (TA) spectroscopy to elucidate the charge transfer pathway within a blend of the donor polymer PM6 and NFAs. Interestingly, the charge carrier lifetimes of neat Y6 and BTP-eC9 are comparable, both reaching up to 20 ns. However, the PM6:BTP-eC9 blend exhibits substantially higher charge carrier generation and a longer carrier lifetime compared to PM6:Y6 blend films, leading to superior performance. By comparing TA data obtained from PM6:Y6 or PM6:BTP-eC9 blend films with and without processing additives, we observe significantly enhanced charge carrier generation and prolonged charge carrier lifetimes in the presence of these additives. These findings underscore the potential of manipulating excited species as a promising avenue for further enhancing the performance of organic solar cells. Moreover, this understanding contributes to the advancement of NFA-based systems and the optimization of charge transfer processes in polymer:NFA blends.

Exciton-Scissoring Perfluoroarenes Trigger Photomultiplication in Full Color Organic Image Sensors.

An unprecedented but useful functionality of perfluoroarenes to enable exciton scissoring in photomultiplication-type organic photodiodes (PM-OPDs) is reported. Perfluoroarenes that are covalently connected to polymer donors via a photochemical reaction enable the demonstration of high external quantum efficiency and B-/G-/R-selective PM-OPDs without the use of conventional acceptor molecules. The operation mechanism of the suggested perfluoroarene-driven PM-OPDs, how covalently bonded polymer donor:perfluoroarene PM-OPDs can perform as effectively as polymer donor:fullerene blend-based PM-OPDs, is investigated. By employing a series of arenes and conducting steady-state/time-resolved photoluminescence and transient absorption spectroscopy analyses, it is found that interfacial band bending between the perfluoroaryl group and polymer donor is responsible for exciton scissoring and subsequent electron trapping, which induces photomultiplication. Owing to the acceptor-free and covalently interconnected photoactive layer in the suggested PM-OPDs, superior operational and thermal stabilities are observed. Finally, finely patterned B-/G-/R-selective PM-OPD arrays that enable the construction of highly sensitive passive matrix-type organic image sensors are demonstrated.

Ultra-Narrowband Near-Infrared Responsive J-Aggregates of Fused Quinoidal Tetracyanoindacenodithiophene.

Narrowband photoresponsive molecules are highly coveted in high-resolution imaging, sensing, and monochromatic photodetection, especially those extending into the near-infrared (NIR) spectral range. Here, a new class of J-aggregating materials based on quinoidal indacenodithiophenes (IDTs) that exhibit an ultra-narrowband (full width half maxima of 22 nm) NIR absorption peak centered at 770 nm is reported. The spectral width is readily tuned by the length of the solubilizing alkyl group, with longer chains resulting in significant spectral narrowing. The J-aggregate behavior is confirmed by a combination of excited state lifetime measurements and single-crystal X-ray diffraction measurements. Their utility as electron-transporting materials is demonstrated in both transistor and phototransistor devices, with the latter demonstrating good response at NIR wavelengths (780 nm) over a range of intensities.

Covalent Networking of a Conjugated-Polymer Photocatalyst to Promote Exciton Diffusion in the Aqueous Phase for Efficient Hydrogen Production.

A conjugated polymer particle in an aqueous phase is covalently networked in 3D by crosslinking with azide groups, leading to significantly enhanced activity-a high photocatalytic H2 evolution rate (11 024 µmol g-1 h-1 (λ > 420 nm)) and a high apparent quantum yield (up to 0.8%). The reaction between the photoactive azide and the alkyl chains of the conjugated polymer provides more intact intermolecular polymeric interactions in the colloidal state, thus preventing physical swelling and inhibiting the recombination of photoproduced carriers. The covalent network efficiently promotes exciton diffusion, which greatly facilitates charge separation and transfer. The azide photo-crosslinking also leads to more compact and better-packed nanoparticles in the aqueous phase and efficient transfer of excitons to the outer surface of the nanoparticles, where photocatalytic reactions occur. These results show that photo-crosslinking can suppress the adverse effects of alkyl chains which inhibit photocatalytic performance. Therefore, covalent crosslinking is a promising strategy for the development of solar and hydrogen energy.