{"title":"Low-Cost Fused-Ring Electron Acceptors for Efficient Organic Solar Cells by Fine-Tuning Molecular Crystallization and Film Formation Kinetics.","authors":"Wenkui Wei,Xiyue Yuan,Xia Zhou,Yao Li,Seunglok Lee,Jinqun Xu,Yue Zhang,Haozhe Feng,Qiuju Jiang,Jiaying Wu,Changduk Yang,Xiaotao Hao,Fei Huang,Yong Cao,Chunhui Duan","doi":"10.1002/anie.202517485","DOIUrl":"https://doi.org/10.1002/anie.202517485","url":null,"abstract":"Achieving high power conversion efficiencies (PCEs) with low-cost active layer materials is of vital importance for organic solar cell (OSC) commercialization. However, the PCEs afforded by currently reported low-cost electron acceptors remain substantially limited. Herein, we report the regulation of molecular crystallization and film formation kinetics of the low-cost electron acceptors with A-DA'D-A-type pentacyclic fused-ring structures and achieved an impressive PCE of 18.04% and a tiptop figure-of-merit (FOM) of 0.363, representing the best-known values for OSCs. Single crystal X-ray diffraction studies indicate that the long and flexible side chain on the central core could hinder the unfavorable dimer formation of electron acceptors and lead to three-dimensional network packing, which is critical for exciton diffusion and charge transport. Moreover, the in situ optical spectroscopy revealed that the side chain elongation of the electron acceptor could slow the film formation kinetics of the small molecular acceptor while accelerating those of the polymer donor, which is conducive to forming bi-continuous interpenetrating fibril networks with better intermixing. This work demonstrates that low-cost, simple-structured fused-ring electron acceptors hold a bright future in the OSC commercialization.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"114 1","pages":"e202517485"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jie Guo,Xu-Hang Zhong,Li Rao,Bing-Zhe Wang,Zhuo Chen,Yu Zhang,Tao Wu,Sónia A C Carabineiro,Li-Li Wen,Chun-Ying Duan
{"title":"Anthraquinone-Based Donor-Acceptor Covalent Organic Frameworks with Thiazole Linkages to Enhance Direct Hydrogen Atom Transfer and Charge Separation in Photocatalytic Oxidation of C(sp3)─H Bonds.","authors":"Jie Guo,Xu-Hang Zhong,Li Rao,Bing-Zhe Wang,Zhuo Chen,Yu Zhang,Tao Wu,Sónia A C Carabineiro,Li-Li Wen,Chun-Ying Duan","doi":"10.1002/anie.202517694","DOIUrl":"https://doi.org/10.1002/anie.202517694","url":null,"abstract":"The design of efficient covalent organic frameworks (COFs) as photocatalysts for C(sp3)─H bond oxidation under green and mild conditions is highly desirable. Herein, TpAQ-TZ COF and TpAR-TZ COF, featuring thiazole linkages, were synthesized by combining 1,3,5-tricarboxylcarboxaldehyde (Tp), sulfur (S8), and direct hydrogen atom transfer (d-HAT) components (2,6-diaminoanthraquinone, AQ; 2,6-diaminoanthrone, AR). The TpAQ-TZ COF demonstrates impressive photocatalytic activity, achieving a 93% yield for phthalan oxidation under heterogeneous conditions-a rare example of photocatalytic C(sp3)─H bond oxidation in water under ambient conditions. Theoretical calculations reveal enhanced hydrogen atom abstraction capability coming from the increased number of d-HAT catalytic sites. Moreover, BdAQ-TZ COF and HbAQ-TZ COF were prepared by replacing Tp with 2,4-dihydroxy-1,3,5-triformylbenzene (Bd) or 2-hydroxy-1,3,5-triformylbenzene (Hb), respectively. Dipole moment calculations and femtosecond transient absorption spectroscopy show that the increased number of hydroxyl groups on the benzene-1,3,5-tricarbaldehyde monomer improves the charge separation efficiency within the three COFs, thereby accounting for the enhanced photocatalytic activity of TpAQ-TZ COF. This work opens up new opportunities for designing highly active photocatalysts by using the synergistic effects of d-HAT, O2 •-, and 1O2 within anthraquinone-based donor-acceptor COF platforms, offering a sustainable route for the oxidation of C(sp3)─H bonds under environmentally friendly conditions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"120 1","pages":"e202517694"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pingping Zheng,Linjie Li,Lixiao Guo,Weibo Cui,Chenglong Li
{"title":"One-Step Carbonyl-Locking Strategy for Multi-Resonance Emitters Enabling Efficient, Narrowband Blue OLEDs.","authors":"Pingping Zheng,Linjie Li,Lixiao Guo,Weibo Cui,Chenglong Li","doi":"10.1002/anie.202518419","DOIUrl":"https://doi.org/10.1002/anie.202518419","url":null,"abstract":"Efficient and narrowband blue multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters are highly attractive for wide color gamut organic light-emitting diodes (OLEDs). Here, we strategically incorporate an electron-deficient carbonyl lock at the para-position of the nitrogen atom in the classical MR-TADF skeleton by a simple one-step carbonylation reaction with a high yield. Compared to the parent molecules, this design strategy not only reduces intramolecular charge-transfer intensity, leading to blue-shifted emission, but also effectively enhances molecular planarity and rigidity, thereby narrowing the emission spectra. As a result, the proof-of-concept emitters, namely CO-BCzBN and CO-DABNA, are developed, with emission peaks at 462 and 445 nm, and narrow the full widths at half maximum (FWHMs) of 16 and 18 nm, respectively, representing the first blue boron/nitrogen/carbonyl hybrid MR-TADF emitters. The sensitized OLEDs based on CO-BCzBN and CO-DABNA achieve excellent blue electroluminescent performance, with the maximum external quantum efficiency (EQEmax) values of 37.9% and 22.8%, along with the Commission Internationale de l'Éclairage (CIE) coordinates of (0.133, 0.141) and (0.146, 0.078), respectively.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"94 1","pages":"e202518419"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209314","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jan Hobich,Xingyu Wu,Florian Feist,Willie Scheibel,Natalia Herdt,Paul Somers,Eva Blasco,Hatice Mutlu,Christopher Barner-Kowollik
{"title":"Synergistic Two-Color Photochemical Polymer Network Formation and Lithography.","authors":"Jan Hobich,Xingyu Wu,Florian Feist,Willie Scheibel,Natalia Herdt,Paul Somers,Eva Blasco,Hatice Mutlu,Christopher Barner-Kowollik","doi":"10.1002/anie.202518815","DOIUrl":"https://doi.org/10.1002/anie.202518815","url":null,"abstract":"We introduce synergistic two-color lithography as an advanced wavelength-gated strategy for spatially and temporally controlling polymer network formation. Our photoresist entails two photoswitches, i.e., diarylindenone epoxide (DIO) and strained azobenzene (SA), each activated at a judiciously selected wavelength, i.e., 375 or 430 nm. Under specific conditions of photon flux, simultaneous irradiation at both wavelengths induces a (3 + 2) cycloaddition between the photoactivated DIO' and SA' species, generating covalently crosslinked networks, whereas under these specifically determined conditions, single-wavelength exposure does not induce solidification. Kinetic analysis highlights the potential of synergistic activation to enable advanced additive manufacturing. We implemented the two-color activated covalent bond forming system in a dual-laser lithographic platform enabling the fabrication of well-defined structures, including segmented ring and butterfly architectures by simply activating and deactivating one of the colors of light.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"75 1","pages":"e202518815"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Tubular All-Benzene Nanocarbon with Evolving Excited-State Chirality.","authors":"Gaolei Li,Xueli Wang,Liang-Liang Mao,Jia-Nan Gao,Xueliang Shi,Hongwei Li,Zi-Tong Li,Zi-Ye Huo,Yiming Chen,Hai-Bo Yang,Jinquan Chen,Chen-Ho Tung,Li-Zhu Wu,Huan Cong","doi":"10.1002/anie.202518587","DOIUrl":"https://doi.org/10.1002/anie.202518587","url":null,"abstract":"Molecular nanocarbons with precisely defined conjugated scaffolds can provide an ideal platform for investigating mechanistic insights into photophysical properties. Here, we report the synthesis and time-resolved spectroscopic characterization of two isomeric tubular all-benzene nanocarbon (TANC) molecules, named meso- and chiral-TANC, respectively. Structurally, they feature triple covalent linkages, with different connectivity, between coaxially stacked cycloparaphenylene units. While meso-TANC maintains conformational rigidity, chiral-TANC shows photo-induced dynamic helicity. Femtosecond transient absorption (TA) and time-resolved circularly polarized luminescence (TRCPL) spectroscopy demonstrate that chiral-TANC undergoes ultrafast relaxation accompanied by untwisting motions within 8 ps upon photoexcitation, establishing the direct correlation between photo-induced conformational evolution and chiroptical dynamics in heteroatom-free, fully conjugated molecules.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"98 1","pages":"e202518587"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209305","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yang An,Xuhao Yang,Ruilin Wang,Yu Gu,Yulin Min,Tierui Zhang,Jinyou Shen,Kan Zhang
{"title":"Improving Tandem Epoxidation Efficiency via Hydrogel Confinement Effect towards Photoelectrochemical Propylene Oxide Synthesis.","authors":"Yang An,Xuhao Yang,Ruilin Wang,Yu Gu,Yulin Min,Tierui Zhang,Jinyou Shen,Kan Zhang","doi":"10.1002/anie.202518020","DOIUrl":"https://doi.org/10.1002/anie.202518020","url":null,"abstract":"Propylene oxide (PO) is among the world's most abundantly produced commodity chemicals, but it suffers from an energy-intensive and highly polluting industrial production route. In this work, we present a tandem photoelectrochemical (PEC) PO production system involving water oxidation to H2O2 via a BiVO4 photoanode and subsequent propylene epoxidation by titanium silicalite-1 (TS-1) catalyst-loaded hydrogel using in situ-generated H2O2. The hydrogel encapsulated on the BiVO4 photoanode surface provides a confined space to enhance H2O2 enrichment, as well as propylene transport, thereby reinforcing the epoxidation kinetics with conversion efficiencies of 94.06% for H2O2 and 75.55% for propylene. With the assistance of solar energy, the PO productivity per unit of electricity can reach 6.10 mol·cm-2·kWh-1, which is the lowest electricity consumption for existing alkene epoxidation technology. For industrial scalability, a multi-pass light absorption configuration is designed for decimeter-sized reactor to address the issue of a plunge in solar to chemical (STC) efficiency arising from the scale-up of the photoanode, achieving the optimum light harvesting efficiency of 98.21% and STC efficiency of 5.57% which is comparable to its 1 cm2 counterpart (86% retention). The continuous PO productivity in flowing electrolyte can reach 1.74 mmol·h-1 with a steady selectivity of 91.05% under AM 1.5G illumination. Finally, a techno-economic analysis is provided to offer targets that need to be met for economically compelling industrial implementation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"2 1","pages":"e202518020"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Dual-Ligand Regulation of Homogeneous Cation-Anion Distribution Enables Efficient and Stable Perovskite Solar Cells.","authors":"Kunpeng Li,Zuolin Zhang,Xinlong Zhao,Tao Wang,Zhishan Li,Huicong Zhang,Dongfang Li,Fashe Li,Yuling Zhai,Hua Wang,Xing Zhu,Cong Chen,Jiangzhao Chen,Tao Zhu","doi":"10.1002/anie.202518592","DOIUrl":"https://doi.org/10.1002/anie.202518592","url":null,"abstract":"While amidine ligands are known to significantly enhance defect passivation in perovskite solar cells (PSCs), their role in modulating perovskite film homogeneity through coordinated control of cation-anion distributions remains unexplored. Herein, we demonstrate that a dual-ligand strategy utilizing pyridine-2-carboximidamide hydrochloride (PCH) and pyridine-2,6-dicarboximidamide dihydrochloride (PBD) achieves homogeneous cation-anion distributions, enabling high-performance PSCs. Incorporated into the precursor solutions, these dual-ligand additives distribute uniformly throughout the perovskite bulk. By simultaneously utilizing their pyridine and amidine groups to passivate Pb2⁺ and FA⁺ ions, as well as employing hydrogen bonding to stabilize I- ions, the uniformity of anions and cations within the film is enhanced. Vacuum flash-assisted solution-processed PSCs incorporating PBD-passivated films with optimized homogeneity achieved a PCE of 26.66% (certified 26.33%). Notably, these devices retained over 90% of their initial efficiency after 1100 h of continuous maximum power point tracking (MPPT) under operational conditions (60 °C, N2 atmosphere). This PCE value ranks among the highest reported to date for perovskite solar cells. Our findings highlight that achieving homogeneous cation-anion distribution is essential for designing effective passivators, thereby simultaneously advancing both the PCE and operational stability of PSCs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"25 1","pages":"e202518592"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209337","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Organic-Acid-Mediated Growth of Oriented Membrane from 2D-Structured Zirconium MOF for CO2 Separation.","authors":"Yonghui Lin,Junchao Dong,Qi Zhou,Hao Zhang,Haicheng Jiang,Ziyang Wang,Xu Zhao,Guojian Ren,Qinhe Pan,Guangshan Zhu,Xiaoqin Zou","doi":"10.1002/anie.202519421","DOIUrl":"https://doi.org/10.1002/anie.202519421","url":null,"abstract":"Two-dimensional structured metal-organic framework (2D-structured MOF) membranes with functionalized and ordered-direction pores hold significant promise for efficient CO2 separation. However, the direct synthesis of such membranes remains a substantial challenge. Herein, we report a novel organic-acid-mediated conversion strategy for direct transformation of a preformed metal-organic gel (MOG) into an oriented membrane of 2D-structured MOF. The MOG is initially synthesized and subsequently dissociated to release Zr6 clusters, which promotes the nucleation and growth of the MOF structure. Small organic molecules of formic acid are employed to modulate the coordination between Zr6 clusters and 4,4',4″-tricarboxyltriphenylamine ligand (TCA3-). By finely tuning the balance between crystallization and intergrowth kinetics, a highly oriented Zr-TCA membrane is fabricated, exhibiting excellent crystallinity and structural homogeneity. The resulting Zr-TCA membrane features nitrogen-functionalized, well-aligned pores oriented parallel to the direction of gas permeation; enabling outstanding CO2/N2 separation performance, with an exceptional CO2 permeance of 1857.3 GPU and a high CO2/N2 selectivity of 39.2 at 0.12 MPa and 25 °C.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":"e202519421"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209044","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Iron-Catalyzed Highly Stereospecific Glycosylation with Glycal Epoxides.","authors":"Xiao-Wen Zhang,Le Yin,Dakang Zhang,Zixiang Jiang,Pinzhi Wang,Hao Xu","doi":"10.1002/anie.202517634","DOIUrl":"https://doi.org/10.1002/anie.202517634","url":null,"abstract":"Complex carbohydrates are essential to understanding life processes, but their synthesis is still challenging. In principle, complex glycans could be rapidly assembled via reiterative and stereospecific glycosylation with glycal epoxides. However, the existing stereospecific glycosylation methods with glycal epoxides are ineffective for the vast majority of secondary sugar acceptors, because they often induce irreversible glycal epoxide decomposition and concurrent SN1-type glycosylation, affording an inseparable mixture of diastereomeric glycosylation products in low yields. We report herein a new catalytic, highly stereospecific glycosylation method for glycal epoxides using readily available iron catalysts. This method is effective for a wide variety of glycal epoxides and glycosyl acceptors, including previously challenging, sterically hindered secondary acceptors and electron-deficient glucuronic ester epoxides. It also facilitates the assembly of an array of biologically important glycosidic linkages that were previously difficult to obtain in high stereoselectivity. Kinetic studies revealed that this iron-catalyzed glycosylation proceeds through SN2-type pathways with both primary and hindered secondary acceptors.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"114 1","pages":"e202517634"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Blue Organic Long Persistent Luminescence: A UV/Violet-Light-Excitable and Green/Red-Light-Erasable Donor-Sensitizer-Acceptor Organic Afterglow System.","authors":"Wen Xia,Zi Ye,Guoyi Wu,Honghong Yao,Hongxin Gao,Biao Xu,Qianhui Chong,Kaka Zhang","doi":"10.1002/anie.202518387","DOIUrl":"https://doi.org/10.1002/anie.202518387","url":null,"abstract":"We pioneered a donor-sensitizer-acceptor three-component system to devise organic long persistent luminescence (OLPL) materials, where the afterglow color is solely determined by sensitizer's emission color. Here we report two major breakthroughs in the field of OLPL: 1) tailored fabrication of pure-blue OLPL materials and 2) a direct observation of OLPL erased by green/red lights. We rationally designed blue thermally activated delayed fluorescence (TADF) sensitizers by connecting biphenyl-containing group with suitable HOMO and T1 energy levels to difluoroboron β-diketonate moiety based on the energy gap law and the El-Sayed rule. The resultant donor-sensitizer-acceptor three-component materials exhibit pure-blue hour-long OLPL afterglow with λOLPL < 450 nm; such pure-blue OLPL materials remain elusive in the reported studies. Mechanistic investigations confirm a unique charge-separation-induced OLPL pathway, involving electron transfer processes between donor, sensitizer, and acceptor. The OLPL materials are UV/visible-light-excitable. Remarkably, it is found that the OLPL emission can be erased by green or red light; the long-lived excited TADF sensitizers can be pushed by green/red lights to higher excited states, followed by fast nonradiative deactivation, enabling optical erasure. This unprecedented optical write-erase functionality, coupled with hour-long OLPL duration, would offer promising opportunities for rewritable photonic storage, encryption, and dynamic labeling applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"120 1","pages":"e202518387"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209315","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}