Organic Halides Research Articles

Crystal Structure and Optical Properties Characterization in Quasi-0D Lead-Free Bromide Crystals (C6H14N)3Bi2Br9·H2O and (C6H14N)3Sb3Br12.

Low dimensional organic inorganic metal halide materials have shown broadband emission and large Stokes shift, making them widely used in various fields and a promising candidate material. Here, the zero-dimensional lead-free bromide single crystals (C6H14N)3Bi2Br9·H2O (1) and (C6H14N)3Sb3Br12 (2) were synthesized. They crystallized in the monoclinic crystal system with the space group of P21 and P21/n, respectively. Through ultraviolet-visible-near-infrared (UV-vis-NIR) absorption analysis, the band gaps of (C6H14N)3Bi2Br9·H2O and (C6H14N)3Sb3Br12 are found to be 2.75 and 2.83 eV, respectively. Upon photoexcitation, (C6H14N)3Bi2Br9·H2O exhibit broad-band red emission peaking at 640 nm with a large Stokes shift of 180 nm and a lifetime of 2.94 ns, and the emission spectrum of (C6H14N)3Sb3Br12 are similar to those of (C6H14N)3Bi2Br9·H2O. This exclusive red emission is ascribed to the self-trapping exciton transition caused by lattice distortion, which is confirmed through both experiments and first-principles calculations. In addition, due to the polar space group structure and the large spin-orbit coupling (SOC) associated with the heavy elements of Bi and Br of crystal 1, an obvious Rashba effect was observed. The discovery of organic inorganic metal bromide material provides a critical foundation for uncovering the connection between 0D metal halide materials' structures and properties.

A Non-Bonding Interaction-Based Fluorescent Probe for Detection of Halogenated Carbonyl Compounds

The fluorescent detection of neutral and volatile carbonyl halogenated compounds had not been studied before. We describe here a simple and sensitive turn-on rhodamin fluorescent probe for the selective detection of fluorinated/brominated/chlorinated/iodinated carbonyl compounds. A wide range of linear or cyclic volatile organic halides was detected with a limit of detection as low as 45.6 nM within 1 min. Mechanistic experiments and DFT calculations indicate the reversible formation of a 1:1 complex of sensor and analyst through non-bonding interaction.

Carboiodanation of Arynes: Organoiodine(III) Compounds as Nucleophilic Organometalloids.

Organic iodine(III) compounds represent the most widely used hypervalent halogen compounds in organic synthesis, where they typically perform the role of an electrophile or oxidant to functionalize electron-rich or -nucleophilic organic compounds. In contrast to this convention, we discovered their unique reactivity as organometallic-like nucleophiles toward arynes. Equipped with diverse transferable ligands and supported by a tethered spectator ligand, the organoiodine(III) compounds undergo addition across the electrophilic C-C triple bond of arynes while retaining the trivalency of the iodine center. This carboiodanation reaction can forge a variety of aryl-alkynyl, aryl-alkenyl, and aryl-(hetero)aryl bonds along with the concurrent formation of an aryl-iodine(III) bond under mild conditions. The newly formed aryl-iodine(III) bond serves as a versatile linchpin for downstream transformations, particularly as an electrophilic reaction site. The amphoteric nature of the iodine(III) group as a metalloid and a leaving group in this sequence enables the flexible and expedient synthesis of extended π-conjugated molecules and privileged biarylphosphine ligands, where all of the iodine(III)-containing compounds can be handled as air- and thermally stable materials.

Impact of Thermal Stabilization on Nutritional, Functional, and Molecular Properties of Six Different Cultivars of Wheat Bran

Background: Wheat bran is an important by-product in the cereal industry. It is considered one of the amplest and most economically cheap sources of insoluble fiber and is rich in minerals and various bioactive compounds. Objective: In this research, the antioxidant, functional, and molecular properties of bran were screened in six different cultivars of wheat, viz. HUW-234, PBW-373, WH-1105, PBW-502, HD-2967, and PBW-343. Methods: In the present study, the methods, namely, DPPH, TPC, and FRAP, were used for the screening of antioxidant properties, bulk density, WAC and OAC for functional properties, and tannin, trypsin inhibitor and phytate for anti-nutritional properties. Results: Our results showed that in thermally processed wheat bran (Autoclaved, Hot air oven, Microwave, Toasting), the antioxidant activity increased in comparison to native wheat bran, whereas water absorption capacity and oil absorption capacity decreased significantly (p ≤ 0.05) compared to native bran. In addition, a significant reduction in the anti-nutritional factor was also observed. Moreover, FTIR in different wheat bran cultivars showed the presence of the C-H group, -CH stretch, -NH group, -OH group, phenols group, -C=O group, mostly aldehyde group, L-glucose, cyclodextrins, –C-OH bending vibrations, and halogen compound (C-Cl). Conclusion: The study showed differences in antioxidant and functional properties of bran obtained from different wheat cultivars. The thermal technique is a very useful treatment for increasing nutritional properties. Wheat bran utilization in daily life helps prevent many chronic diseases, such as colon cancer, constipation, heart disease, etc.

Electrocatalytic Reduction of Benzyl Bromide during Single Ag Nanoparticle Collisions.

Previous reports of the electrocatalytic activity of Ag nanoparticles (AgNPs) toward the reduction of organic halides have been limited to measurements of immobilized nanoparticle ensembles. Here, we have investigated the electrochemical reduction of benzyl bromide (PhCH2Br) occurring at single AgNPs (4.2 to 37 nm radius) in methanol, where the effects of nanoparticle size on catalytic behavior can be more thoroughly examined and rigorously quantified. AgNP collisions at a 6.3 μm radius Au ultramicroelectrode (UME) result in measurable electrocatalytic amplification currents from the reduction of PhCH2Br, where collision events are indicated by a sudden step increase in the reduction current recorded in the current-time trace. The dependence of the height of these steps on the applied potential allowed for an analysis of reaction kinetics based on the Butler-Volmer model, resulting in an estimation of the standard rate constant (k0) as a function of AgNP size. Measured values of k0 range from 4.0 × 10-4 to 8.0 × 10-4 cm/s on AgNPs with radii of 14, 29, and 37 nm, whereas k0 was found to be 6.2 × 10-4 cm/s at a 12.3 μm radius Ag disk UME. The results indicate that the kinetics of PhCH2Br reduction are independent of AgNP size and are similar to the reaction kinetics observed at a Ag UME. The frequency of observed particle collisions was found to be dependent on particle size, where 14 nm radius AgNPs resulted in the highest-frequency collisions. The potential- and size-dependent interactions of AgNPs with the Au UME are discussed in terms of the DLVO theory.

Microencapsulated Perovskite Crystals via In Situ Permeation Growth from Polymer Microencapsulation-Expansion-Contraction Strategy: Advancing a Record Long-Term Stability beyond 10000 h for Perovskite Solar Cells.

Organic metal halide perovskite solar cells (PSCs) bearing both high efficiency and durability are predominantly challenged by inadequate crystallinity of perovskite. Herein, a polymer microencapsulation-expansion-contraction strategy is proposed for the first time to optimize the crystallization behavior of perovskite, typically by adeptly harnessing the swelling and deswelling characteristics of poly(4-acryloylmorpholine) (poly(4-AcM)) network on PbI2 surface. It can effectively retard the crystallization rate of perovskite, permitting meliorative crystallinity featured by increased grain size from 0.74 to 1.32µm and reduced trap density from 1.12 × 1016 to 2.56 × 1015 cm-3. Moreover, profiting from the protection of poly(4-AcM) microencapsulation layer, the degradation of the perovskite is markedly suppressed. Resultant PSCs gain a robust power conversion efficiency (PCE) of 24.04%. Typically, they maintain 91% of their initial PCE for 13008 h in a desiccated ambient environment and retain 92% PCE after storage for 4000 h with a relative humidity of 50 ± 10%, which is the state-of-the-art long-term stability among the reported contributions.

Mechanochemical synthesis of organoselenium compounds

We disclose herein a strategy for the rapid synthesis of versatile organoselenium compounds under mild conditions. In this work, magnesium-based selenium nucleophiles are formed in situ from easily available organic halides, magnesium metal, and elemental selenium via mechanical stimulation. This process occurs under liquid-assisted grinding (LAG) conditions, requires no complicated pre-activation procedures, and operates broadly across a diverse range of aryl, heteroaryl, and alkyl substrates. In this work, symmetrical diselenides are efficiently obtained after work-up in the air, while one-pot nucleophilic addition reactions with various electrophiles allow the comprehensive synthesis of unsymmetrical monoselenides with high functional group tolerance. Notably, the method is applied to regioselective selenylation reactions of diiodoarenes and polyaromatic aryl halides that are difficult to operate via solution approaches. Besides selenium, elemental sulfur and tellurium are also competent in this process, which showcases the potential of the methodology for the facile synthesis of organochalcogen compounds.

Feasibility Study on the Generation of Nanoporous Metal Structures by Means of Selective Alloy Depletion in Halogen-Rich Atmospheres.

A new approach to produce nanoporous metals has been investigated, which is based on the dealloying of bi- or multi-component alloys. Depletion and pore formation of the alloy substrate are obtained by the transport of certain alloy components at high temperatures via volatile halogen compounds. These halogen compounds are transferred to materials acting as sinks based on their higher affinity to the respective components, and chemically bound there. Transfer via volatile halogen compounds is known from the pack cementation coating process and from high-temperature corrosion in certain industrial atmospheres. The approach was tested on different precursor alloys: Ti-43.5Al-4Nb-1Mo-0.1B (TNM-B1), TiNb42, and AlCu. Both dealloying effects and micro-scale pore formation were observed. The detailed size of the porous structures is in the range of 50 nm for both TNM-B1 and TiNB42 and 500 nm for AlCu.

N‐Heterocyclic Carbenes (NHCs)‐Catalyzed Coupling Reactions of Aldehydes and Organic Halides

AbstractThis concept aims to summarize the direct coupling of aldehydes and organic halides (including activated and unactivated organic halides) catalyzed by N‐heterocyclic carbenes (NHCs). The key factor of this transformation is the formation of Breslow intermediates, which are either nucleophilic or reductive. Additionally, the activation of inert C−H bond also was reviewed in this performance via the processes of single electron transfer (SET) and subsequent intramolecular 1,n‐ hydrogen atom transfer (HAT) or intermolecular HAT. Finally, the key differences and reactivity of various Breslow intermediates, generated from different NHCs, have been discussed to give a deeper understanding of the ongoing popularity of NHC‐organocatalysis.

Interfacial Tuning of Electrocatalytic Ag Surfaces for Fragment-Based Electrophile Coupling.

Construction of C‒C bonds in medicinal chemistry frequently draws on the reductive coupling of organic halides with ketones or aldehydes. Catalytic C(sp3)‒C(sp3) bond formation, however, is constrained by the competitive side reactivity of radical intermediates following sp3 organic halide activation. Here, an alternative paradigm deploys catalytic Ag surfaces for reductive fragment-based electrophile coupling compatible with sp3 organic halides. We use in-situ spectroscopy, electrochemical analyses, and simulation to uncover the catalytic interfacial structure and guide reaction development. Specifically, Mg(OAc)2 outcompetes the interaction between Ag and the aldehyde, thereby tuning the Ag surface for selective product formation. Data are consistent with an increased population of Mg-bound aldehyde facilitating the addition of a carbon-centered radical (product of Ag-electrocatalyzed organic halide reduction) to the carbonyl. Electron transfer from Ag to the resultant alkoxy radical yields the desired alcohol. Molecular interfacial tuning at reusable catalytic electrodes will accelerate development of sustainable organic synthetic methods.

Aggregation-induced emission organic metal halide complex for X-ray scintillation.

The expanding applications of X-ray scintillation across various areas, from healthcare to security detection call for the development of new-generation scintillators that offer enhanced sensitivity, efficiency, and versatility. Here, we report for the first time the use of organic metal halide complexes with aggregation-induced emission (AIE) for X-ray scintillation, which can be facilely synthesized and processed in the solution phase. By reacting an AIE organic molecule, 4-(4-(diphenylamino) phenyl)-1-(propyl)-pyridinium (TPA-PD) with zinc chloride (ZnCl2) in solution at room temperature, an organic metal halide complex, (TPA-PD)2ZnCl2, is produced with a high synthetic yield of 87%. Optical and radioluminescence characterizations find that (TPA-PD)2ZnCl2 exhibits bluish-green photoluminescence and radioluminescence peaked at around 450 nm, with a photoluminescence quantum efficiency (PLQE) of 65%, and an absolute light yield of 13 423 Photon per MeV. Moreover, short photoluminescence and radioluminescence decay lifetimes are recorded at 1.81 ns and 5.24 ns, respectively. For X-ray scintillation, an excellent response dose-response linearity and a low limit of detection of 80.23 nGyair S-1 are obtained for (TPA-PD)2ZnCl2. By taking advantage of the high X-ray absorption of metal halides and fast radioluminescence of AIE molecules, our design of covalently bonded organic metal halide complexes opens up new opportunities for the development of high-performance solution-processable scintillators.

Tunable luminescence based on structural regulation in organic antimony halides for X-ray scintillation

Organic antimony halides show high photoluminescence quantum yield (PLQY) due to their compositional and structural tunability, which provides the possibility for developing high quantum yield scintillators.

Aromatization-driven deconstructive functionalization of spiro dihydroquinazolinones via dual photoredox/nickel catalysis.

Aromatization-driven deconstruction and functionalization of spiro dihydroquinazolinones via dual photoredox/nickel catalysis is developed. The aromatization effect was introduced to synergistically drive unstrained cyclic C-C bond cleavage, with the aim of overcoming the ring-size limitation of nitrogen-centered radical induced deconstruction of carbocycles. Herein, we demonstrate the synergistic photoredox/nickel catalyzed deconstructive cross-coupling of spiro dihydroquinazolinones with organic halides. Remarkably, structurally diverse organic halides including aryl, alkenyl, alkynyl, and alkyl bromides were compatible for the coupling. In addition, this protocol is also characterized by its mild and redox-neutral conditions, excellent functional group compatibility, high atom economy, and easy scalability. A telescoped procedure involving condensation and ring-opening/coupling was found to be accessible. This work provides a complementary strategy to the existing radical-mediated C-C bond cleavage of unstrained carbocycles.

Synthesis and application of well-defined [Ph4P]+[Cu(CF2CF3)2]- complex as a versatile pentafluoroethylating reagent.

We herein describe the preparation and application of a new bispentafluoroethylated organocuprate [Ph4P]+[Cu(CF2CF3)2]-. This complex has demonstrated a remarkable range of reactivities towards carboxylic acids, diazonium salts, organic halides, boronic esters, terminal alkynes and (hetero)arenes as a versatile pentafluoroethylating reagent. The construction of C(sp3)-/C(sp2)-/C(sp)-CF2CF3 bonds can therefore be achieved using a single reagent.

Mechanochemical generation of aryl barium nucleophiles from unactivated barium metal.

Organobarium reagents are of interest as homologues of the Grignard reagents based on organomagnesium compounds due to their unique reactivity as well as regio- and stereoselectivity. However, reactions involving organobarium reagents are less developed in comparison to reactions involving Grignard reagents due to the lack of a simple and economical synthetic method and their high reactivity. To the best of our knowledge, there is no established method for the direct synthesis of organobarium compounds from commercially available bulk barium metal and organic halides. So far, the generation of organobarium compounds usually requires the use of activated barium (Rieke barium), which significantly reduces the practical utility of organobarium reagents and hinders the development of new organobarium-mediated transformations. Here, we present a mechanochemical strategy based on ball-milling that facilitates the direct generation of various aryl barium nucleophiles from commercially available unactivated barium metal and aryl halides without complicated pre-activation processes. Our simple mechanochemical protocol allows the rapid development of novel carbon-silicon-bond-forming reactions with hydrosilanes mediated by aryl barium nucleophiles; importantly, these reactions are difficult to achieve using other Grignard-type carbon nucleophiles. To the best of our knowledge, this is the first example of a nucleophilic substitution reaction involving an aryl barium species. Furthermore, this mechanochemical strategy established the first example of a nucleophilic addition to a carbonyl compound involving an aryl barium nucleophile. Preliminary theoretical calculations using the artificial force-induced reaction (AFIR) method to reveal the reaction mechanism of the hydrosilane arylation are also described.

A core-shell model of polymetallic hybrid metal halides.

Most polymetallic hybrid metal halides are assumed to show a homogenous distribution of the metal ions in the bulk. Herein, we demonstrate a core-shell model for the hybrid lead halide [(C6H18N3)2·Pb2Br10] (C6H18N3 = 2-(piperazin-1-yl)ethan-1-aminium) coated with a manganese bromide layer. This model can explain the different photoemission of this composite material, and provides new insights on the investigation of polymetallic low-dimensional organic metal halides.

Synthesis and luminescence mechanism of 1D organic metal halides with mixed single-stranded and double-stranded chains

The composition of the single- and double-stranded chain mixed structures increases the level of octahedral distortion and alters the band structure, thereby facilitating the recombination of carriers and significantly enhancing the PLQY.

On the prospects of high-entropy organic A-site halide perovskites.

High entropy is a hot topic in materials research due to several interesting and surprising phenomena, of which one crucial aspect is entropic stabilization. As well-known materials for optoelectronic and electrochemical applications, halide perovskites (HPs) suffer from instability issues and would benefit greatly from increased configurational entropy. Despite that, only a few literature reports have connected HPs with the concept of high-entropy materials. Furthermore, mixing A-site cations, especially organic ones, to achieve maximized configurational entropies has not been explored in detail either in experimental or computational works. Aiming to obtain high-entropy organic A-site HPs, we synthesized and characterized a system of penta-organic A-site cations HP of general formula GAxFAxEAxACxMA1-4xPbI3. Results on the structure and phase transitions show that single-phase solid solutions can be obtained for x values up to almost 0.08, resulting in one of the highest configurational entropies ever reported in A-site-only mixed HPs. The high-entropy HPs also showed band gaps of about 1.5 eV, decreased ionic transport, and remarkable stability compared to the unsubstituted composition. The results consolidate the potential of maximizing the configurational entropy as a design parameter in HPs.

Ultrafast and high-resolution X-ray imaging based on zero-dimensional organic silver halides

Supersensitive and fast X-ray imaging is of great importance in medical diagnosis, industrial flaw detection, security and safety inspection, and frontier science exploration.

Organohalogenochromism (OHC) of D–π–A pyridinium dye polymer films and the colorimetric detection of volatile organic halogen compounds

We propose that polymeric organohalogenochromic dyes are one of the most promising and convenient functional materials for the colorimetric detection of volatile organohalogen compounds (VOHCs), including CH2Cl2 and CHCl3.