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| Open AccessScalable, highly stable Si-based metal-insulator-semiconductor photoanodes for water oxidation fabricated using thin-film reactions and electrodeposition
Authors demonstrate Si-based MIS photoanodes using Al thin-film reactions to create localized conduction paths through the insulator and Ni electrodeposition to form metal catalyst islands. These approaches yielded low onset potential, high saturation current density, and excellent stability.
- Soonil Lee
- , Li Ji
- & Edward T. Yu
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Article
| Open AccessWittichenite semiconductor of Cu3BiS3 films for efficient hydrogen evolution from solar driven photoelectrochemical water splitting
A highly efficient, stable, low-cost and environmentally friendly photocathode is the goal of practical solar hydrogen evolution applications. Here, authors report a Cu3BiS3-based photocathode and Cu3BiS3-BiVO4 tandem cell for unbiased overall solar water splitting with a STH efficiency over 2%.
- Dingwang Huang
- , Lintao Li
- & Feng Jiang
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Article
| Open AccessCharge carrier mapping for Z-scheme photocatalytic water-splitting sheet via categorization of microscopic time-resolved image sequences
The Z-scheme photocatalytic system is promising for producing renewable energy by sunlight, but the optimization of multiple materials is challenging. Here, authors directly map out the photocatalytic activity on a microscopic scale by the clustering analysis for the time-resolved image sequence.
- Makoto Ebihara
- , Takeshi Ikeda
- & Kenji Katayama
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Article
| Open AccessMechanistic analysis of multiple processes controlling solar-driven H2O2 synthesis using engineered polymeric carbon nitride
Solar-driven H2O2 production presents a renewable approach to chemical synthesis. Here, authors perform a mechanistic analysis on the contribution of the sodium cyanaminate moiety to the 2-electron oxygen reduction reaction performance of polymeric carbon nitride frameworks.
- Yubao Zhao
- , Peng Zhang
- & Wonyong Choi
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Article
| Open AccessUltrafast coherent motion and helix rearrangement of homodimeric hemoglobin visualized with femtosecond X-ray solution scattering
Femtosecond time-resolved X-ray solution scattering (fs-TRXSS) measurements provide information on the structural dynamics of proteins in solution. Here, the authors present a structure refinement method for the analysis of fs-TRXSS data and use it to characterise the ultrafast structural changes of homodimeric haemoglobin.
- Yunbeom Lee
- , Jong Goo Kim
- & Hyotcherl Ihee
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Article
| Open AccessPhotocatalyzed cycloaromatization of vinylsilanes with arylsulfonylazides
Arene-fused siloles have attracted interest due to their promising applications in electronic and optoelectronic devices. Here, the authors report Ir(III)-catalyzed cycloaromatization of ortho-alkynylaryl vinylsilanes with arylsulfonyl azides via α-silyl radical Smiles rearrangement for accessing naphthyl-fused benzosiloles under visible-light photoredox conditions.
- Fengjuan Chen
- , Youxiang Shao
- & Wei Zeng
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Article
| Open AccessVisible-light photoredox-catalyzed umpolung carboxylation of carbonyl compounds with CO2
Compounds bearing a carbonyl group, such as aldehydes and ketones, are important industrial chemicals and widespread in pharmaceuticals and natural products. Here, the authors report a strategy for visible-light photoredox-catalyzed umpolung carboxylation of diverse carbonyl compounds with CO2, to generate valuable α-hydroxycarboxylic acids.
- Guang-Mei Cao
- , Xin-Long Hu
- & Da-Gang Yu
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Article
| Open AccessBarrier-free reverse-intersystem crossing in organic molecules by strong light-matter coupling
Strong coupling of organic materials with optical cavities allows to manipulate the rate of energy transfer between their internal states. Here, the authors show a hybrid state of singlet character with energy lower than the triplet state, and a flow of energy from the triplet to the hybrid state.
- Yi Yu
- , Suman Mallick
- & Karl Börjesson
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Article
| Open Access2,6-diaminopurine promotes repair of DNA lesions under prebiotic conditions
UV-induced photodamage that likely occurred during the prebiotic synthesis of DNA and RNA is still an untackled issue for their origin on early Earth. Here, the authors show that substitution of 2,6-diaminopurine for adenine enables repair of cyclobutane pyrimidine dimers with high yields, and demonstrate that both 2,6-diaminopurine and adenine nucleosides can be formed under the same prebiotic conditions.
- Rafał Szabla
- , Magdalena Zdrowowicz
- & Janusz Rak
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Article
| Open AccessEfficient 3D printing via photooxidation of ketocoumarin based photopolymerization
3D printing enables customized manufacturing that is difficult to achieve through traditional material processing but 3D printing with high resolution and high speed is challenging to realize. Here, the authors demonstrate that photooxidation of a ketocoumarin photosensitizer can simultaneously deliver high print speed and high print resolution on a common 3D printer.
- Xiaoyu Zhao
- , Ye Zhao
- & Xiaolin Xie
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Article
| Open AccessThree body photodissociation of the water molecule and its implications for prebiotic oxygen production
Three-body dissociation of water, producing one oxygen and two hydrogen atoms, has been difficult to investigate due to the lack of intense vacuum ultraviolet sources. Here, using a tunable free-electron laser, the authors obtain quantum yields for this channel showing that it is a possible route to prebiotic oxygen formation in interstellar environments.
- Yao Chang
- , Yong Yu
- & Xueming Yang
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Article
| Open AccessPhotocatalytic three-component asymmetric sulfonylation via direct C(sp3)-H functionalization
The direct and selective C(sp3)-H functionalization of cycloalkanes and alkanes is useful in organic synthesis but its application to asymmetric catalysis has been less explored. Here, the authors demonstrate the incorporation of a dual asymmetric photocatalyst which leads to the development of asymmetric sulfonylation involving direct functionalization of cycloalkanes, alkanes, toluene derivatives or ethers.
- Shi Cao
- , Wei Hong
- & Lei Gong
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Article
| Open AccessPhotoactivatable metabolic warheads enable precise and safe ablation of target cells in vivo
Metabolites can distinguish pathogenic from healthy cells, but they are hard to couple to current photosensitizers without altering their biological activity. Here the authors design a new family of photosensitizers that retain metabolite function to target pathogenic cells and ablate them by photodynamic therapy.
- Sam Benson
- , Fabio de Moliner
- & Marc Vendrell
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Article
| Open AccessPromoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore
Designing highly efficient chromophores comprising earth-abundant elements is essential for both light harvesting and electron transfer reactions. Here, authors prepare a copper purpurin complex that shows enhanced photocatalytic activity for CO2 reduction to CO with a high selectivity.
- Huiqing Yuan
- , Banggui Cheng
- & Zhiji Han
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Article
| Open AccessPhotolytic radical persistence due to anoxia in viscous aerosol particles
Sunlight can change the composition of atmospheric aerosol particles, but the mechanisms through which this happens are not well known. Here, the authors show that fast radical reaction and slow diffusion near viscous organic particle surfaces can cause oxygen depletion, radical trapping and humidity dependent oxidation.
- Peter A. Alpert
- , Jing Dou
- & Markus Ammann
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Article
| Open AccessAdjusting the energy of interfacial states in organic photovoltaics for maximum efficiency
Understanding the mechanism of non-radiative losses in organic photovoltaics is crucial to improve the performance further. Here, the authors use combined device and spectroscopic data to reveal universal model to maximise exciton splitting and charge separation by adjusting the energy of charge transfer state.
- Nicola Gasparini
- , Franco V. A. Camargo
- & Christoph J. Brabec
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Article
| Open AccessPredicting wavelength-dependent photochemical reactivity and selectivity
Predicting the conversion and selectivity of a photochemical reactions is challenging. Here, the authors introduce a framework for the quantitative prediction of the time-dependent progress of a photoligation reaction and predict LED-light induced conversion through a wavelength-resolved numerical simulation.
- Jan P. Menzel
- , Benjamin B. Noble
- & Christopher Barner-Kowollik
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Article
| Open AccessDual Ni/photoredox-catalyzed asymmetric cross-coupling to access chiral benzylic boronic esters
Metallaphototoredox catalysis has been rarely applied to reductive cross-couplings, in contrast to typical redox-neutral methods. Here, the authors report a mild Ni/photoredox-catalyzed reductive cross-coupling of aryl iodides and α-chloroboranes, further enriching the metallaphotoredox chemistry.
- Purui Zheng
- , Pan Zhou
- & Tao XU
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Article
| Open AccessProbing intramolecular vibronic coupling through vibronic-state imaging
Vibronic coupling is a key feature of molecular electronic transitions, but its visualization in real space is an experimental challenge. Here the authors, using scanning tunneling microscopy induced luminescence, resolve the effect of vibronic coupling with different modes on the electron distributions in real space in a single pentacene molecule.
- Fan-Fang Kong
- , Xiao-Jun Tian
- & J. G. Hou
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Article
| Open AccessSequential cocatalyst decoration on BaTaO2N towards highly-active Z-scheme water splitting
Activation of narrow-bandgap photocatalysts holds key to applicable solar-to-hydrogen energy conversion. Here, the authors demonstrate effective sequential cocatalyst decoration for such narrow-bandgap photocatalysts to realise highly-efficient hydrogen evolution and Z-scheme water splitting.
- Zheng Wang
- , Ying Luo
- & Kazunari Domen
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Article
| Open AccessGeneral synthetic strategy for regioselective ultrafast formation of disulfide bonds in peptides and proteins
Synthesis of peptides and proteins containing multiple disulfide bonds is challenging, limiting the elucidation of their biological functions. Here, the authors report a general synthetic strategy for fast formation of two and three disulfide bonds in peptides and proteins, and apply it to prepare several therapeutically important peptides.
- Shay Laps
- , Fatima Atamleh
- & Ashraf Brik
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Article
| Open AccessFacile electron delivery from graphene template to ultrathin metal-organic layers for boosting CO2 photoreduction
While solar-to-fuel energy conversion is appealing, materials require accessible active sites for reactants and rapid electron transfer steps. Here, authors support ultrathin metal-organic layers with graphene oxide as both template and electron mediator to boost CO2 photoreduction performance.
- Jia-Wei Wang
- , Li-Zhen Qiao
- & Tong-Bu Lu
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Article
| Open AccessHalo-fluorescein for photodynamic bacteria inactivation in extremely acidic conditions
Photodynamic inactivation is a common antibacterial method but often fails in extremely acidic environments (pH< 4). Here, the authors demonstrate halogenation of fluorescein for the development of a photodynamic agent which works in extremely acidic environments and demonstrate sterilisation applications in fruit juice and in vivo.
- Ying Wang
- , Jiazhuo Li
- & Peng Wu
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Article
| Open AccessUnravelling an oxygen-mediated reductive quenching pathway for photopolymerisation under long wavelengths
Photomediated-reversible-deactivation radical polymerisation has a limited scope of available photocatalysts due to multiple stringent requirements of properties. Here the authors show, an oxygen-mediated reductive quenching pathway for photoinduced electron transfer reversible addition-fragmentation chain transfer polymerisation.
- Chenyu Wu
- , Kenward Jung
- & Cyrille Boyer
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Article
| Open AccessMetal-free atom transfer radical polymerization with ppm catalyst loading under sunlight
Organocatalytic atom transfer radical polymerization (O-ATRP) is attractive due to its metal-free nature but catalysts are rarely applied at a low loading. Here the authors introduce a catalyst design logic based on heteroatom-doping of polycyclic arenes, which led to the discovery of oxygen-doped anthanthrene as an organic photoredox catalysts for O-ATRP.
- Qiang Ma
- , Jinshuai Song
- & Saihu Liao
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Article
| Open AccessLong wavelength single photon like driven photolysis via triplet triplet annihilation
The use of short wavelength light in photolysis applications in chemistry and biology is limited by photolytic reaction yields, photodamage and photobleaching. Here, the authors report a general long wavelength single photon driven photolysis method using a triplet-triplet annihilation process.
- Ling Huang
- , Le Zeng
- & Gang Han
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Article
| Open AccessAtomically thin photoanode of InSe/graphene heterostructure
Achieving efficient photoelectrochemical cells requires insights into the ion kinetics at the surface of photoelectrode. Here, the authors show a new platform for investigating strong coupling between hydroxide ions and surface charge carriers by using monolayer InSe as the anode with high photocurrent density.
- Haihong Zheng
- , Yizhen Lu
- & Yang Cao
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Article
| Open AccessA droplet microfluidic platform for high-throughput photochemical reaction discovery
Translating discovery scale vial-based batch reactions to continuous flow scale-up conditions is limited by significant time and resource constraints. Here, the authors report a photochemical droplet microfluidic platform, which enables high throughput reaction discovery in flow to generate pharmaceutically relevant compound libraries.
- Alexandra C. Sun
- , Daniel J. Steyer
- & Corey R. J. Stephenson
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Article
| Open AccessTwo-dimensional electronic spectroscopy of bacteriochlorophyll a with synchronized dual mode-locked lasers
Multidimensional electronic spectroscopy techniques still have many limitations. Here, the authors introduce a 2D electronic spectroscopy technique that uses broadband, synchronized mode-locked lasers to study dynamics on a wide range of timescales.
- JunWoo Kim
- , Jonggu Jeon
- & Minhaeng Cho
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Article
| Open AccessSilicon and oxygen synergistic effects for the discovery of new high-performance nonfullerene acceptors
Developing a new π-skeletal aromatic fused-ring for tuning material properties in organic electronics is still a challenge due to limited chemical approach. Here, the authors enrich the chemistry by synthesizing SiO-bridged ladder-type π-skeletons with enhanced planarity and deeper energy levels than CO-bridged counterpart.
- Ying Qin
- , Hui Chen
- & Dongbing Zhao
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Article
| Open AccessSequentially amplified circularly polarized ultraviolet luminescence for enantioselective photopolymerization
Chiral functional materials with circularly polarized luminescence can be used in various applications but rarely reported. Here the authors show, a complex system, which show intense circularly polarized ultraviolet luminescence with large glum value, enabling a chiral UV light triggered enantioselective polymerization.
- Dongxue Han
- , Xuefeng Yang
- & Pengfei Duan
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Article
| Open AccessLong-lived and disorder-free charge transfer states enable endothermic charge separation in efficient non-fullerene organic solar cells
Designing efficient organic solar cells is limited by the energy required to overcome the mutual Coulomb attraction between electron and hole. Here, the authors reveal long-lived and disorder-free charge-transfer states enable efficient endothermic charge separation in non-fullerene systems with marginal energy offset.
- Ture F. Hinrichsen
- , Christopher C. S. Chan
- & Philip C. Y. Chow
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Article
| Open AccessUniversal and versatile morphology engineering via hot fluorous solvent soaking for organic bulk heterojunction
Morphology control of bulk heterojunction organic solar cells has been a challenge for realising optimal photovoltaic performance. Here, the authors utilise amphiphobic nature and temperature-dependent miscibility of fluorous solvent to promote molecular reorganisation and morphological optimisation.
- Tong Shan
- , Yi Zhang
- & Hongliang Zhong
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Article
| Open AccessPhotobase effect for just-in-time delivery in photocatalytic hydrogen generation
Efficient photocatalytic hydrogen generation relies on highly choreographed delivery of protons and electrons to the reaction site such that they arrive just in time. Here, authors show that proton transport can be controlled by light with the photobase effect to increase H2 generation rate.
- Jiawen Fang
- , Tushar Debnath
- & Jacek K. Stolarczyk
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Article
| Open AccessRationally designed transition metal hydroxide nanosheet arrays on graphene for artificial CO2 reduction
The development of effective, earth-abundant cocatalysts is critical for photocatalytic CO2 reduction. Here, authors report the assembly of transition metal hydroxides on graphene to act as cocatalyst ensembles for efficient CO2 photoreduction.
- Kang-Qiang Lu
- , Yue-Hua Li
- & Yi-Jun Xu
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Article
| Open AccessHigh-performance light-driven heterogeneous CO2 catalysis with near-unity selectivity on metal phosphides
There exists an urgent need to develop new materials to convert CO2 to useful products. Here, authors demonstrate metal phosphide nanoparticles to enable light-driven CO2 hydrogenation with high activities and near-unity selectivity.
- Yang-Fan Xu
- , Paul N. Duchesne
- & Geoffrey A. Ozin
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Article
| Open AccessWide range zero-thermal-quenching ultralong phosphorescence from zero-dimensional metal halide hybrids
Molecular luminescence is generally significantly quenched at high temperature. Here the authors report a zero-dimensional metal halide hybrid that exhibits zero-thermal-quenching ultralong phosphorescence over a wide temperature range of 220 K, and demonstrate use for Morse code encryption and logic gates.
- Shuya Liu
- , Xiaoyu Fang
- & Dongpeng Yan
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Perspective
| Open AccessDesigning and understanding light-harvesting devices with machine learning
Photon-induced charge separation phenomena are at the heart of light-harvesting applications but challenging to be described by quantum mechanical models. Here the authors illustrate the potential of machine-learning approaches towards understanding the fundamental processes governing electronic excitations.
- Florian Häse
- , Loïc M. Roch
- & Alán Aspuru-Guzik
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Article
| Open AccessProbing nanoscale spatial distribution of plasmonically excited hot carriers
Revealing the spatial distribution of hot carriers in real space is crucial to their efficient utilization. Here, the authors show that in-situ electrochemical tip-enhanced Raman spectroscopy is able to resolve the spatial distribution of reactive hot carriers with a nanometer spatial resolution.
- Sheng-Chao Huang
- , Xiang Wang
- & Bin Ren
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Article
| Open AccessKinetic prediction of reverse intersystem crossing in organic donor–acceptor molecules
Understanding and predicting the kinetics of reverse intersystem crossing (RISC) facilitates the design of materials. Here, the authors demonstrate a theoretical expression that reproduces experimental RISC rate constants ranging over five orders of magnitude in selected molecules.
- Naoya Aizawa
- , Yu Harabuchi
- & Yong-Jin Pu
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Article
| Open AccessDetection of the thietane precursor in the UVA formation of the DNA 6-4 photoadduct
The mechanisms of formation of the (6-4) photoproducts in DNA damage by sunlight is still debated. Here the authors show, by optical spectroscopies and computations, the details of the formation of a (6-4) photoadduct via the thietane intermediate in a single-stranded DNA oligonucleotide.
- Luis A. Ortiz-Rodríguez
- , Christian Reichardt
- & Carlos E. Crespo-Hernández
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Article
| Open AccessPhotocatalytic hydrogen peroxide splitting on metal-free powders assisted by phosphoric acid as a stabilizer
While H2 can serve as a renewable fuel, its large scale production, storage, and transport are challenging. Here, authors show H2O2 to serve as a potential energy carrier via the photocatalytic production of H2 from stabilized H2O2 solutions and metal-free catalysts.
- Yasuhiro Shiraishi
- , Yuki Ueda
- & Takayuki Hirai
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Article
| Open AccessEffects of nonequilibrium fluctuations on ultrafast short-range electron transfer dynamics
Ultrafast electron-transfer reactions are fundamental to protein functions. Here the authors show that these reaction dynamics are affected by the ruggedness of protein energy landscape, which even modifies the reaction free energy and reorganization energy.
- Yangyi Lu
- , Mainak Kundu
- & Dongping Zhong
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Article
| Open AccessCathode engineering with perylene-diimide interlayer enabling over 17% efficiency single-junction organic solar cells
It is desired to design cathode interfacial layers to simultaneously improve the efficiency and stability of organic solar cells and tune the cathode properties. Here, Yao et al. develop such interfacial layers for the best donor-acceptor system and achieve a high certified efficiency close to 17%.
- Jia Yao
- , Beibei Qiu
- & Yongfang Li
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Article
| Open AccessPhotoinduced monooxygenation involving NAD(P)H-FAD sequential single-electron transfer
The number of usable light-responsive enzymes is limited, despite the potential biotechnological applications. Here, the authors report a flavoprotein monooxygenase which is controllable by blue light illumination, and propose a mechanism involving protein-mediated radical photoreduction of FAD via a semiquinone intermediate.
- Simon Ernst
- , Stefano Rovida
- & Steffen L. Drees
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Article
| Open AccessSelf-regulating photochemical Rayleigh-Bénard convection using a highly-absorbing organic photoswitch
Autonomous control of liquid motion is vital to the development of new actuators and pumps in fluid systems but autonomous control of fluid motion is inaccessible in current systems. Here, the authors identify unique features of a photochromic molecular switch that enables its use for self-regulating light activated control of fluid flow.
- Serena Seshadri
- , Luke F. Gockowski
- & Megan T. Valentine
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Article
| Open AccessIntegrated redox-active reagents for photoinduced regio- and stereoselective fluorocarboborylation
The synthesis of vinylboronates and alkylboronates often suffers from step-tedious and poorly stereoselective procedures. Here, the authors report a bench-stable redox-active reagent for the radical difunctionalization of alkenes and alkynes affording fluorine-containing vinylboronates and alkylboronates.
- Weigang Zhang
- , Zhenlei Zou
- & Yi Pan
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Article
| Open AccessUnique hole-accepting carbon-dots promoting selective carbon dioxide reduction nearly 100% to methanol by pure water
Solar-driven CO2 reduction by abundant water to alcohols is hindered by the sluggish water oxidation reaction. Here, the authors demonstrate that the microwave-synthesized carbon-dots possess unique hole-accepting nature, allowing stoichiometric oxygen and methanol production from water and CO2 with nearly 100% selectivity to methanol.
- Yiou Wang
- , Xu Liu
- & Junwang Tang
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Article
| Open AccessAncillary ligand increases the efficiency of heteroleptic Ir-based triplet emitters in OLED devices
Though Ir-based dopants with ancillary ligands are attractive for realizing efficient organic light-emitting diodes, a strategy for designing these materials remains elusive. Here, the authors report a design strategy for heteroleptic triplet OLED emitters featuring functionalized ancillary ligands.
- Seung-yeol Baek
- , Seung-Yeon Kwak
- & Mu-Hyun Baik