Delocalizing Excitation for Highly-Active Organic Photovoltaic Catalysts.

Localized excitation in traditional organic photocatalysts typically prevents the generation and extraction of photo-induced free charge carriers, limiting their activity enhancement under illumination. Here, we enhance delocalized photoexcitation of small molecular photovoltaic catalysts by weakening their electron-phonon coupling via rational fluoro-substitution. The optimized 2FBP-4F catalyst we develop here exhibits a minimized Huang-Rhys factor of 0.

Organic Photovoltaic Catalyst with Extended Exciton Diffusion for High-Performance Solar Hydrogen Evolution.

The short exciton diffusion length () associated with most classical organic photocatalysts (5-10 nm) imposes severe limits on photocatalytic hydrogen evolution efficiency. Here, a photovoltaic molecule (F1) without electron-deficient units at the central building block was designed and synthesized to improve the photoluminescence quantum yield (PLQY). With the enhanced PLQY of 9.

Enhancing Transition Dipole Moments of Heterocyclic Semiconductors via Rational Nitrogen-Substitution for Sensitive Near Infrared Detection.

Designing ultrastrong near-infrared (NIR) absorbing organic semiconductors is a critical prerequisite for sensitive NIR thin film organic photodetectors (OPDs), especially in the region of beyond 900 nm, where the absorption coefficient of commercial single crystalline silicon (c-Si) is below 10 cm . Herein, a pyrrolo[3,2-b]thieno[2,3-d]pyrrole heterocyclic core (named as BPPT) with strong electron-donating property and stretched geometry is developed. Relative to their analogue Y6, BPPT-contained molecules, BPPT-4F and BPPT-4Cl, show substantially upshifted and more delocalized highest occupied molecular orbitals, and larger transition dipole moments, leading to bathochromic and hyperchromic absorption spectra extending beyond 1000 nm with very large absorption coefficients (up to 3.

Revealing the Sole Impact of Acceptor's Molecular Conformation to Energy Loss and Device Performance of Organic Solar Cells through Positional Isomers.

Two new fused-ring electron acceptor (FREA) isomers with nonlinear and linear molecular conformation, m-BAIDIC and p-BAIDIC, are designed and synthesized. Despite the similar light absorption range and energy levels, the two isomers exhibit distinct electron reorganization energies and molecular packing motifs, which are directly related to the molecular conformation. Compared with the nonlinear acceptor, the linear p-BAIDIC shows more ordered molecular packing and higher crystallinity.

Pushing the Efficiency of High Open-Circuit Voltage Binary Organic Solar Cells by Vertical Morphology Tuning.

The tuning of vertical morphology is critical and challenging for organic solar cells (OSCs). In this work, a high open-circuit voltage (V ) binary D18-Cl/L8-BO system is attained while maintaining the high short-circuit current (J ) and fill factor (FF) by employing 1,4-diiodobenzene (DIB), a volatile solid additive. It is suggested that DIB can act as a linker between donor or/and acceptor molecules, which significantly modifies the active layer morphology.

Symmetrically Fluorinated Benzo[1,2-:4,5-']dithiophene-Cored Donor for High-Performance All-Small-Molecule Organic Solar Cells with Improved Active Layer Morphology and Crystallinity.

Side-chain engineering is an efficient molecular design strategy for morphology optimization and performance improvement of organic solar cells (OSCs). Herein, a novel small-molecule donor C-2F, which owns a benzo[1,2-:4,5-']dithiophene (BDT) central unit with a symmetrically difluorinated benzene ring as a conjugated side chain, has been synthesized. The conjugated side chain possesses both the symmetry and halogenation effect in novel small molecular donor material.

Asymmetric Glycolated Substitution for Enhanced Permittivity and Ecocompatibility of High-Performance Photovoltaic Electron Acceptor.

Traditional organic photovoltaic materials exhibit low dielectric constants (ε) of 3 to 4, restricting the further enhancement of power conversion efficiencies (PCEs) of organic solar cells (OSCs). Herein we design and synthesize a fused-ring electron acceptor named Y6-4O through introducing an asymmetric highly polarizable oligo(ethylene glycol) side chain onto the pyrrole unit of Y6. Compared with alkylated Y6 (ε = 3.

Uncovering the out-of-plane nanomorphology of organic photovoltaic bulk heterojunction by GTSAXS.

The bulk morphology of the active layer of organic solar cells (OSCs) is known to be crucial to the device performance. The thin film device structure breaks the symmetry into the in-plane direction and out-of-plane direction with respect to the substrate, leading to an intrinsic anisotropy in the bulk morphology. However, the characterization of out-of-plane nanomorphology within the active layer remains a grand challenge.

An Electron Acceptor Analogue for Lowering Trap Density in Organic Solar Cells.

Typical organic semiconductor materials exhibit a high trap density of states, ranging from 10 to 10  cm , which is one of the important factors in limiting the improvement of power conversion efficiencies (PCEs) of organic solar cells (OSCs). In order to reduce the trap density within OSCs, a new strategy to design and synthesize an electron acceptor analogue, BTPR, is developed, which is introduced into OSCs as a third component to enhance the molecular packing order of electron acceptor with and without blending a polymer donor. Finally, the as-cast ternary OSC devices employing BTPR show a notable PCE of 17.

Enhancing Open-Circuit Voltage of High-Efficiency Nonfullerene Ternary Solar Cells with a Star-Shaped Acceptor.

The ternary strategy has been widely used in high-efficiency organic solar cells (OSCs). Herein, we successfully incorporated a mid-band-gap star-shaped acceptor, FBTIC, as the third component into the PM6/Y6 binary blend film, which not only achieved a panchromatic absorption but also significantly improved the open-circuit voltage () of the devices due to the high-lying lowest unoccupied molecular orbital (LUMO) of the FBTIC. Morphology characterizations show that star-shaped FBTIC molecules are amorphously distributed in the ternary system, and the finely tuned ternary film morphology facilitates the exciton dissociation and charge collection in ternary devices.

Selenium Heterocyclic Electron Acceptor with Small Urbach Energy for As-Cast High-Performance Organic Solar Cells.

Typical organic photovoltaic materials show high Urbach energies (ca. 25-50 meV), which is considerably higher than those of their inorganic counterparts and limits further improvement in the device efficiency of organic solar cells (OSCs). In this study, we introduce a facile method of selenium substitution to reduce the Urbach energy of organic photovoltaic materials to 20.

Nickel(0)-Catalyzed Inert C-O Bond Functionalization: Organo Rare-Earth Metal Complex as the Coupling Partner.

An organo rare-earth metal complex has been employed as a highly efficient nucleophile in Ni(0)-catalyzed C-O bond functionalization. The optimized catalytic system which consists of Ni(cod), PCy, and t-BuONa could smoothly convert 1 equiv of naphthyl ethers to alkylated naphthalene analogues with 0.4 equiv of Ln(CHSiMe)(THF), delivering good to excellent yields.

Pd-Catalyzed C(sp)-C(sp) cross-coupling of Y(CHSiMe)(THF) with vinyl bromides and triflates.

Pd-Catalyzed C(sp)-C(sp) cross-coupling of Y(CHSiMe)(THF) with vinyl bromides and triflates has been developed for efficient synthesis of various allyltrimethylsilanes. The cross-coupling reaction was conducted at room temperature with low catalyst loading of either Pd(PPh) or Pd(PPh)Cl, and exhibited high efficiency and a broad substrate scope. In combination with the cross-coupling by the Lewis-acid catalyzed Hosomi-Sakurai reaction, a novel three-component one-pot cascade reaction was then accomplished to deliver homoallylic alcohols and ethers with high regioselectivity and diastereoselectivity.

Palladium-catalyzed C(sp(3))-C(sp(2)) cross-coupling of homoleptic rare-earth metal trialkyl complexes with aryl bromides: efficient synthesis of functionalized benzyltrimethylsilanes.

The first C(sp(3))-C(sp(2)) cross-coupling of rare-earth metal alkyl complexes with aryl bromides has been developed. This reaction was conducted at low catalyst loading (0.5 mol%) and exhibited a broad substrate scope, thus providing a facile method for the synthesis of benzyltrimethylsilanes with diverse functional groups.