Organic Halides Research Articles

Surface defect passivation by copper incorporation for efficient perovskite solar cells

Defects play an important character in the degradation processes of hybrid halide perovskite, hindering their application for solar cells. Ion transport is facilitated by the ubiquitous organic cation and halide anion vacancy defects, which lead to perovskite disintegration at grain boundaries. In this article, a thorough investigation of the vacancy defect and defect density on perovskite is conducted by using VASP and SCAPS-1D. From SCAPS-1D, the PCE of the device increases from 17.82 % to 23.04 % when the defect state density drops from 10+15 to 10+14 cm-3. Therefore, reducing the defect density is very important to improve the performance of perovskite solar cells. Effective perovskite solar cells based on CH3NH3PbI3 incorporated copper ions passivation defects were carried out. Compare to pristine hybrid perovskite, Cu2+-doped hybrid perovskite have remarkably lower trap-state densities, greater film quality, and higher crystallinity. Especially, the maximum power conversion efficiency of up to 20.1 % was achieved with 0.5 % copper ion doping. After 500 h of not being enclosed in dry air, the devices still has 87 % of its original power conversion efficiency. Therefore, this work suggests that careful control the formation of Cu2+ in perovskite films is very important for diverse optoelectronic applications in the future.

Highly efficiency blue emissive from Bi3+ ions in zero-dimensional organic bismuth halide for white LED applications

Zero-dimensional organic-inorganic metal halides (OMHs) attract increasing interest in the fabrication of light-emitting diodes because of their broad emission band and high photoluminescence quantum yield. Thus, almost all OMHs showed green and yellow emissions, while blue was rarely reported. The luminescence mechanism of OMHs was attributed to the self-trapped excitons (STEs), no matter the similar performances between STEs and translations from energy levels of ns2 ions (Sb3+, Bi3+, and Te4+ ions). In this work, zero-dimensional organic tetraphenylphosphonium bismuth chloride TPP2BiCl5 (C48H40P2BiCl5, abbreviated as TBC, TPP=tetraphenylphosphonium.) was synthesized via the antisolvent method The obtained TBC showed the highest efficiency (58%) in blue light emission at 480 nm. While most of the OMHs function according to the STE mechanism, the emission of TBC was confirmed to originate from the 3P1-1S0 transition of Bi3+ ions. The white light-emitting diodes (WLEDs) with a color rendering index of 81 were fabricated by using a near-ultraviolet (NUV) chip, blue emitting single crystal TBC, green-emitting single crystal TPP2MnCl4 (C48H40P2MnCl4, abbreviated as TMC), and red-emitting single crystal TPP2SbCl5 (C48H40P2SbCl5, abbreviated as TSC). Moreover, the single-component white emission was achieved by doping Mn2+ and Sb3+ ions into the lattice of TBC. This work demonstrates the different emission mechanism of ns2 ions based OMHs, and the great potential of bismuth-based OMHs in the applications of WLEDs.

Predicting the melting point of liquid crystals with directed message passing neural networks

ABSTRACT Liquid crystal (LC) phases must exist in an appropriate temperature range for practical applications and thus the melting point (MP) is a critical design target of LCs. In this work, we have evaluated the performance of directed message passing neural networks trained on a large database of organic molecules (27,000+) in the prediction of a structurally diverse set of 780 LC and LC-like molecules including cyano-, azo-, ester, cyclohexyl- and halogen-containing compounds. Our results show that the model can provide accurate MP predictions for LC and LC-like molecules with an overall Mean Absolute Error (MAE) and Root Mean Square Error (RMSE) of 23°C and 30°C, respectively. Our model provides similar levels of performance with MAEs of 20°C, 20°C, 23°C, 25°C and 24°C for azo, cyclohexyl, ester, halogen and nitrile compounds, respectively, and is most accurate for molecules with MP between 50 and 150°C (MAE = 21°C). We have developed an online tool called LCMelt (v1.0) (lcmelt.streamlit.app) where our model can be used to predict the MP of potential LC candidates before synthesis free of charge.

Metallaphotoredox‐Catalyzed Three‐Component Couplings for Practical Synthesis of Ureas and Carbamates†

Comprehensive SummaryUreas are widely used in drugs, materials and catalysts because of their diamide structure, which can form strong hydrogen bonds. Therefore, it is of great scientific significance to develop efficient and green methods for the synthesis of urea compounds, especially unsymmetrical ureas. Here, we have disclosed novel and highly efficient three‐component coupling reactions of organic halides, sodium cyanate and amines enabled by nickel/photoredox dual catalysis for the preparation of unsymmetrical ureas. The reaction features simple and safe operations, broad substrate scopes, and product diversities. It allows the facile synthesis of N‐aryl/vinyl ureas from readily available, user‐friendly feedstocks under mild conditions (27 examples, 36%—98% yields). In addition, this method is further derived to alcohols as nucleophiles to synthesize a series of carbamates (15 examples, 40%—95% yields). The mechanism experiment shows that the isocyanate produced by the coupling of halide and sodium cyanate may be the key intermediate in this reaction.

New particle formation leads to enhanced cloud condensation nuclei concentrations on the Antarctic Peninsula

Abstract. Few studies have investigated the impact of new particle formation (NPF) on cloud condensation nuclei (CCN) in remote Antarctica, and none has elucidated the relationship between NPF and CCN production. To address that knowledge gap, we continuously measured the number size distribution of 2.5–300 nm particles and CCN number concentrations at King Sejong Station on the Antarctic Peninsula from 1 January to 31 December 2018. Ninety-seven NPF events were detected throughout the year. Clear annual and seasonal patterns of NPF were observed: high concentration and frequency of nucleation-mode particles in summer (December–February: 53 NPF cases) and undetected nucleation-mode particles in winter (June–August: no NPF cases). We estimated the spatial scale of NPF by multiplying the time during which a distinct nucleation mode can be observed at the sampling site by the locally measured wind speed. The estimated median spatial scale of NPF around the Antarctic Peninsula was found to be approximately 155 km, indicating the large scale of NPF events. Air back-trajectory analysis revealed that 80 cases of NPF events were associated with air masses originating over the ocean, followed by sea-ice (12 cases), multiple (3 cases), and land (2 cases) regions. We present and discuss three major NPF categories: (1) marine NPF, (2) sea-ice NPF, and (3) multiple NPF. Satellite estimates for sea-surface dimethylsulfoniopropionate (DMSP; a precursor of gaseous dimethyl sulfide) data showed that the production of oceanic biogenic precursors could be a key component in marine NPF events, whereas halogen compounds released from ice-covered areas could contribute to sea-ice NPF events. Terrestrial sources (wildlife colonies, vegetation, and meltwater ponds) from Antarctica could affect aerosol production in multiple air masses. Out of 97 observed NPF events, 83 cases were characterized by the simultaneous increase in the CCN concentration by 2 %–270 % (median 44 %) in the following 1 to 36 h (median 8 h) after NPF events. Overall, Antarctic NPF events were found to be a significant source of particles with different physical characteristics and related to biogenic sources in and around the Antarctic Peninsula, which subsequently grew to cloud condensation nuclei.

Life cycle assessment of the manufacturing and operation of distillation column for eliminating volatile and organic halogen compounds from process wastewater

Distillation serves as the foremost method for commercial-scale separation of fluid mixtures. Widely applied in wastewater treatment, it is the preferred choice for isolating volatile multi-component mixtures into pure substances. Distillation technology offers notable economic benefits due to its easy implementation, high efficiency, productivity, and robust safety features. This study examines the environmental impacts associated with the production and usage of a distillation, specifically in treating pharmaceutical process wastewater containing organic halogen compounds (AOX). The analysis adopts a 'gate-to-gate' approach, with the specified functional unit (FU) set at 1 kg of treated effluent containing no more than 8 ppm of AOX and less than 1000 mg O2/L of Chemical Oxygen Demand (COD). In this work, Life Cycle Assessment (LCA) is conducted using Product Environmental Footprint (PEF) and Recipe 2016 Endpoint (H) V1.06 methodologies, utilizing the SimaPro V9.3.0.3 software in conjunction with the Ecoinvent V3.8 database. Analysis results have shown the emission of 1.11 × 10–2 kg CO2-eq, in which operational and production processes contribute 91.9% and 8.1%, respectively. To mitigate adverse effects, alternative energy sources, i.e., solar, offshore wind, and onshore wind are integrated into the distillation procedure. The substitution of hard coal with solar, offshore wind, and onshore wind energy displays the potential to significantly reduce climate change impact by 64.3%, 62.9%, and 62.8%, respectively.Article HighlightsDistillation process undergoes a thorough life cycle assessment from production to application.Distillation process requires high energy and emits 1.11 × 10–2 kg CO2-eq per functional unit.The operational phase dominates over 90% in three damage categories: human health, ecosystems, and resources.

Moisture-Resilient Perovskite Solar Cells for Enhanced Stability.

With the rapid rise in device performance of perovskite solar cells (PSCs), overcoming instabilities under outdoor operating conditions has become the most crucial obstacle toward their commercialization. Among stressors such as light, heat, voltage bias, and moisture, the latter is arguably the most critical, as it can decompose metal-halide perovskite (MHP) photoactive absorbers instantly through its hygroscopic components (organic cations and metal halides). In addition, most charge transport layers (CTLs) commonly employed in PSCs also degrade in the presence of water. Furthermore, photovoltaic module fabrication encompasses several steps, such as laser processing, subcell interconnection, and encapsulation, during which the device layers are exposed to the ambient atmosphere. Therefore, as a first step toward long-term stable perovskite photovoltaics, it is vital to engineer device materials toward maximizing moisture resilience, which can be accomplished by passivating the bulk of the MHP film, introducing passivation interlayers at the top contact, exploiting hydrophobic CTLs, and encapsulating finished devices with hydrophobic barrier layers, without jeopardizing device performance. Here, existing strategies for enhancing the performance stability of PSCs are reviewed and pathways toward moisture-resilient commercial perovskite devices are formulated.

Tailoring Ag Electron Donating Ability for Organohalide Reduction: A Bilayer Electrode Design.

Electrochemical reduction of organohalides provides a green approach in the reduction of environmental pollutants, the synthesis of new organic molecules, and many other applications. The presence of a catalytic electrode can make the process more energetically efficient. Ag is known to be a very good electrode for the reduction of a wide range of organohalides. Herein, we examine the elementary adsorption and reaction steps that occur on Ag and the changes that result from changes in the Ag-coated metal, strain in Ag, solvent, and substrate geometry. The results are used to develop an electrode design strategy that can possibly be used to further increase the catalytic activity of pure Ag electrodes. We have shown how epitaxially depositing one to three layers of Ag on catalytically inert or less active support metal can increase the surface electron donating ability, thus increasing the adsorption of organic halide and the catalytic activity. Many factors, such as molecular geometry, lattice mismatches, work function, and solvents, contribute to the adsorption of organic halide molecules over the bilayer electrode surface. To isolate and rank these factors, we examined three model organic halides, namely, halothane, bromobenzene (BrBz), and benzyl bromide (BzBr) adsorption on Ag/metal (metal = Au, Bi, Pt, and Ti) bilayer electrodes in both vacuum and acetonitrile (ACN) solvent. The different metal supports offer a range of lattice mismatches and work function differences with Ag. Our calculations show that the surface of Ag becomes more electron donating and accessible to adsorption when it forms a bilayer with Ti as it has a lower work function and almost zero lattice mismatch with Ag. We believe this study will help to increase the electron donating ability of the Ag surface by choosing the right metal support, which in turn can improve the catalytic activity of the working electrode.

Electric-Field Fluctuations as the Cause of Spectral Instabilities in Colloidal Quantum Dots.

Spectral diffusion (SD) represents a substantial obstacle toward implementation of solid-state quantum emitters as a source of indistinguishable photons. By performing high-resolution emission spectroscopy for individual colloidal quantum dots at cryogenic temperatures, we prove the causal link between the quantum-confined Stark effect and SD. Statistically analyzing the wavelength of emitted photons, we show that increasing the sensitivity of the transition energy to an applied electric field results in amplified spectral fluctuations. This relation is quantitatively fit to a straightforward model, indicating the presence of a stochastic electric field on a microscopic scale, whose standard deviation is 9 kV/cm, on average. The current method will enable the study of SD in multiple types of quantum emitters such as solid-state defects or organic lead halide perovskite quantum dots, for which spectral instability is a critical barrier for applications in quantum sensing.

Triple-halide wide-bandgap perovskites tailored via facile organic halide treatment for high-performance perovskite/Cu(In,Ga)Se2 tandem solar cells

Wide-bandgap (Eg) perovskites (PVSK) are important materials for realizing high-efficiency tandem devices that surpass the efficiency limit of single-junction solar cells. However, they suffer from phase separation and open-circuit voltage (Voc) loss. This study demonstrated a facile fabrication strategy of highly efficient and stable wide-Eg PVSKs through an organic halide surface treatment with formamidinium bromide to CH3NH3PbI3-xClx. The concurrent diffusion of organic cations and halide ions from the surface into bulk PVSK results in the complete conversion of the PVSK crystallinity to a cubic phase, eliminating segregated secondary phases and reducing unreacted PbI2. Br incorporation induces halide redistribution, resulting in the formation of triple-halide wide-Eg PVSK. The complete reconstruction of the bulk and surface of PVSK by surface post-treatment suppresses trap-induced nonradiative recombination and decreases the Urbach tail energy. Inverted PVSK solar cells based on the reconstructed PVSK exhibit enhanced photovoltaic performance with a low Voc deficit and high stability. In addition, we demonstrated a four-terminal (4-T) tandem device based on the triple-halide wide-Eg PVSK as a top cell combining with a Cu(In,Ga)Se2 bottom cell, achieving a power conversion efficiency of 24.5 %.

Exploring the hidden treasures of Nitella hyalina: a comprehensive study on its biological compounds, nutritional profile, and unveiling its antimicrobial, antioxidative, and hypoglycemic properties.

Macroalgae has the potential to be a precious resource in food, pharmaceutical, and nutraceutical industries. Therefore, the present study was carried out to identify and quantify the phyco-chemicals and to assess the nutritional profile, antimicrobial, antioxidant, and anti-diabetic properties of Nitella hyalina extracts. Nutritional composition revealed0.05 ± 2.40% ash content, followed by crude protein (24.66 ± 0.95%), crude fat (17.66 ± 1.42%), crude fiber (2.17 ± 0.91%), moisture content (15.46 ± 0.48%) and calculated energy value (173.50 ± 2.90 Kcal/100g). 23 compounds were identified through GC-MS analysis in ethyl acetate extract, with primary compounds being Palmitic acid, methyl ester, (Z)-9-Hexadecenoic acid, methyl ester, and Methyl tetra decanoate. Whereas 15 compounds were identified in n-butanol extract, with the major compounds being Tetra decanoic acid, 9-hexadecanoic acid, Methyl pentopyranoside, and undecane. FT-IR spectroscopy confirmed the presence of alcoholic phenol, saturated aliphatic compounds, lipids, carboxylic acid, carbonyl, aromatic components, amine, alkyl halides, alkene, and halogen compounds. Moreover, n-butanol contains 1.663 ± 0.768mg GAE/g, of total phenolic contents (TPC,) and 2.050 ± 0.143 QE/g of total flavonoid contents (TFC), followed by ethyl acetate extract, i.e. 1.043 ± 0.961mg GAE/g and 1.730 ± 0.311mg QE/g respectively. Anti-radical scavenging effect in a range of 34.55-46.35% and 35.39-41.79% was measured for n-butanol and ethyl acetate extracts, respectively. Antimicrobial results declared that n-butanol extract had the highest growth inhibitory effect, followed by ethyl acetate extract. Pseudomonas aeruginosa was reported to be the most susceptible strain, followed by Staphylococcus aureus and Escherichia coli, while Candida albicans showed the least inhibition at all concentrations. In-vivo hypoglycemic study revealed that both extracts exhibited dose-dependent activity. Significant hypoglycemic activity was observed at a dose of 300mg/kg- 1 after 6h i.e. 241.50 ± 2.88, followed by doses of 200 and 100mg/kg- 1 (245.17 ± 3.43 and 250.67 ± 7.45, respectively) for n-butanol extract. In conclusion, the macroalgae demonstrated potency concerning antioxidant, antimicrobial, and hypoglycemic properties.

The Tetrel Bonds of Hypervalent Halogen Compounds.

The tetrel bond between PhXF2Y(TF3) (T = C and Si; X = Cl, Br, and I; Y = F and Cl) and the electron donor MCN (M = Li and Na) was investigated at the M06-2X/aug-cc-pVDZ level of theory. As the electronegativity of the halogen atom X increases, the strength of the tetrel bond also increases, but as the electronegativity of the halogen atom Y increases, the strength of the tetrel bond decreases. The magnitude of the interaction energy in most -CF3 complexes was found to be less than 10 kcal/mol, but to exceed 11 kcal/mol for PhClF2Cl(CF3)⋯NCNa. The tetrel bond is greatly enhanced when the -SiF3 group interacts with LiCN or NaCN, with the largest interaction energy approaching 100 kcal/mol and displaying a covalent Si⋯N interaction. Along with this enhancement, the Si⋯N distance was found to be less than the X-Si bond length, the -SiF3 group to be closer to the N atom, and in most -SiF3 systems, the X-Si-F angle to be less than 90°; the -SiF3 group therefore undergoes inversion and complete transfer in some systems.

Scalable Synthesis of Lead‐Free Tetramethylammonium Manganese Halides for Highly Efficient Backlight Displays

AbstractLead‐free halides have emerged as clean candidates for lighting and display applications because of their superior optoelectronic properties and environmental friendliness. As for the commercialization, the simple synthetic process, scaled production, low‐cost, and excellent performance are the upmost factors. In this work, lead‐free tetramethylammonium manganese halides are quantitatively synthesized using a mechanochemical approach, in which [(CH3)4N]2MnCl4 powders show green emission with a photoluminescence quantum yield (PLQY) of 21% and (CH3)4NMnCl3 powders possess red emission with a PLQY of 51%, arising from the intrinsic 4T1(4G) → 6A1(6S) d‐d transition of Mn2+. To further boost the green emission efficiency, the composition engineering strategies by Br/Cl substitution and excess organic halide compensation are developed, achieving a high PLQY of 98% for the obtained [(CH3)4N]2MnBr4 powders. Furthermore, white light emitting diode (WLED) devices are fabricated by combining green [(CH3)4N]2MnBr4 powders with red (CH3)4NMnCl3 powders or single crystals, which exhibit a high luminous efficacy (98.06 or 142.40 lm W−1), wide color gamut (over 100 % of NTSC in CIE 1931), and good operating stability (maintained above 80% efficiency after 176 h). This work suggests ball‐milling as a mass synthesis method for metal halides and provides a new Mn2+‐based phosphor for white LEDs in backlight display applications.

Synergetic Effect of Aluminum Oxide and Organic Halide Salts on Two‐Dimensional Perovskite Layer Formation and Stability Enhancement of Perovskite Solar Cells (Adv. Energy Mater. 39/2023)

Synergetic Effect of Aluminum Oxide and Organic Halide Salts on Two‐Dimensional Perovskite Layer Formation and Stability Enhancement of Perovskite Solar Cells (Adv. Energy Mater. 39/2023)

Testing carbon structures for metal-free catalytic/photocatalytic ozonation to remove disinfection by-product formation potential

Different graphitic carbon structures were prepared and tested for catalytic and photocatalytic ozonation of the precursors of chlorination disinfection by-products to remove their disinfection formation potential (DBPFP). Commercial graphite was submitted to ball milling and two chemical treatments with ammonium nitrate or potassium oxalate to increase its surface area. Additionally, ozonation in gas phase and liquid phase were used to generate surface oxygen groups in these materials and in commercial graphene. All the carbon samples were tested and compared with commercial graphene oxide in the removal of humic acid solutions. The highest catalytic activity during the catalytic/photocatalytic ozonation of humic acid was observed for commercial graphene, ozonated graphene and for graphene oxide; however, this did not result in high DBPFP removal and the instability of the materials was demonstrated. With a moderate catalytic activity but better stability, ball-milled graphite ozonated in liquid phase, was selected for photocatalytic ozonation of real surface water leading to a high DBPFP removal at the conditions tested (88 % 5-HAAs (haloacetic acids), 70 % 4-THMs (trihalomethanes), 70 % AOX (adsorbable organic halides); conditions: semi-batch experiments; 0.5 L volume; 5 mg L−1 O3; Qg = 10 L h−1; DOC0 = 5 mg L−1; pH = 7.8; 180 min under simulated solar radiation with average irradiance 580 W m−2).

The device simulation of MXene-added hole-transport free perovskite solar cells

Perovskite solar cells (PSCs) without hole transport layer (HTL) based on organic and inorganic metal halide perovskite have received vast consideration in recent years. For predigestion of device structure and construction process, the exclusion of the HTL is a marvelous way. By detaching the HTL part of the devices, we could reduce the cost and complexity of the structures. Currently, a novel 2D material named Ti3C2 MXene with high electron mobility, excellent metallic conductivity and functionalized surface groups applied for tuning the energy offsets has been reported to be added in the perovskite absorber layer, leading to a remarkable power conversion efficiency (PCE) improvement. In this work, the role of MXenes in controlling the work function of the involved layers to modify the band alignment towards better performance of the cells is explained. Two HTL free structures of FTO/mTiO2/cTiO2/MAPbI3/Spiro-OMeTAD/Au named as HFRC, and FTO/mTiO2+MXene/cTiO2+MXene/MXene/MAPbI3+MXene/Spiro-OMeTAD/Au named as HFMC were simulated by SCAPS-1D software to study the response of the photovoltaic devices and obtain the highest possible efficiency considering the physics behind. To the best of our knowledge, this is the first time such structures and the results of the current simulation are studied that may be used as a guideline for other practical purposes. We present a modeling procedure that optimizes the thickness of the involved layers and specifies the optimum level of the doping concentration. We also show that by optimizing the work function of the back contact, the device performance witnesses a significant improvement, proving the considerable role of the back contact in these cells. The simulated HTL-free devices illustrate attainably PCEs of about 20.32% and 21.04% for the cells without and with MXene, under AM 1.5G illumination and absorption up to 760 (nm).

Effective Activation of Strong C−Cl Bonds for Highly Selective Photosynthesis of Bibenzyl via Homo‐Coupling

AbstractCarbon‐carbon (C−C) coupling of organic halides has been successfully achieved in homogeneous catalysis, while the limitation, e.g., the dependence on rare noble metals, complexity of the metal‐ligand catalylst and the poor catalyst stability and recyclability, needs to be tackled for a green process. The past few years have witnessed heterogeneous photocatalysis as a green and novel method for organic synthesis processes. However, the study on C−C coupling of chloride substrates is rare due to the extremely high bond energy of C−Cl bond (327 kJ mol−1). Here, we report a robust heterogeneous photocatalyst (Cu/ZnO) to drive the homo‐coupling of benzyl chloride with high efficiency, which achieves an unprecedented high selectivity of bibenzyl (93 %) and yield rate of 92 % at room temperature. Moreover, this photocatalytic process has been validated for C−C coupling of 10 benzylic chlorides all with high yields. In addition, the excellent stability has been observed for 8 cycles of reactions. With detailed characterization and DFT calculation, the high selectivity is attributed to the enhanced adsorption of reactants, stabilization of intermediates (benzyl radicals) for the selective coupling by the Cu loading and the moderate oxidation ability of the ZnO support, besides the promoted charge separation and transfer by Cu species.

Effective Activation of Strong C-Cl Bonds for Highly Selective Photosynthesis of Bibenzyl via Homo-Coupling.

Carbon-carbon (C-C) coupling of organic halides has been successfully achieved in homogeneous catalysis, while the limitation, e.g., the dependence on rare noble metals, complexity of the metal-ligand catalylst and the poor catalyst stability and recyclability, needs to be tackled for a green process. The past few years have witnessed heterogeneous photocatalysis as a green and novel method for organic synthesis processes. However, the study on C-C coupling of chloride substrates is rare due to the extremely high bond energy of C-Cl bond (327 kJ mol-1 ). Here, we report a robust heterogeneous photocatalyst (Cu/ZnO) to drive the homo-coupling of benzyl chloride with high efficiency, which achieves an unprecedented high selectivity of bibenzyl (93 %) and yield rate of 92 % at room temperature. Moreover, this photocatalytic process has been validated for C-C coupling of 10 benzylic chlorides all with high yields. In addition, the excellent stability has been observed for 8 cycles of reactions. With detailed characterization and DFT calculation, the high selectivity is attributed to the enhanced adsorption of reactants, stabilization of intermediates (benzyl radicals) for the selective coupling by the Cu loading and the moderate oxidation ability of the ZnO support, besides the promoted charge separation and transfer by Cu species.

Cross‐Electrophile C−PIIICoupling of Chlorophosphines with Organic Halides: Photoinduced PIIIand Aminoalkyl Radical Generation Enabled by Pnictogen Bonding

AbstractPnictogen bonding (PnB) has gained recognition as an appealing strategy for constructing novel architectures and unlocking new properties. Within the synthetic community, the development of a straightforward and much simpler protocol for cross‐electrophile C−PIIIcoupling remains an ongoing challenge with organic halides. In this study, we present a simple strategy for photoinduced PnB‐enabled cross‐electrophile C−PIIIcouplings using readily available chlorophosphines and organic halides via merging single electron transfer (SET) and halogen atom transfer (XAT) processes. In this photomediated transformation, the PnB formed between chlorophosphines and alkyl amines facilitates the photogeneration of PIIIradicals andα‐aminoalkyl radicals through SET. Subsequently, the resultingα‐aminoalkyl radicals activate C−X bonds via XAT, leading to the formation of carbon radicals. This methodology offers operational simplicity and compatibility with both aliphatic and aromatic chlorophosphines and organic halides.

Cross-Electrophile C-PIII Coupling of Chlorophosphines with Organic Halides: Photoinduced PIII and Aminoalkyl Radical Generation Enabled by Pnictogen Bonding.

Pnictogen bonding (PnB) has gained recognition as an appealing strategy for constructing novel architectures and unlocking new properties. Within the synthetic community, the development of a straightforward and much simpler protocol for cross-electrophile C-PIII coupling remains an ongoing challenge with organic halides. In this study, we present a simple strategy for photoinduced PnB-enabled cross-electrophile C-PIII couplings using readily available chlorophosphines and organic halides via merging single electron transfer (SET) and halogen atom transfer (XAT) processes. In this photomediated transformation, the PnB formed between chlorophosphines and alkyl amines facilitates the photogeneration of PIII radicals and α-aminoalkyl radicals through SET. Subsequently, the resulting α-aminoalkyl radicals activate C-X bonds via XAT, leading to the formation of carbon radicals. This methodology offers operational simplicity and compatibility with both aliphatic and aromatic chlorophosphines and organic halides.