Indium Bromide Research Articles

One-Step Transformation of Aryl Diazonium Salts into Aryl Indium(III) Reagents.

A method for the conversion of diazonium salts into intrinsically nucleophilic aryl indium reagents is described. The reaction is performed using indium(I) bromide with the C-In bond being formed by the interaction of aryl radicals with the indium salt. The obtained aryl indium(III) reagents work well in the Liebeskind-Srogl cross-coupling with thioesters, affording a wide variety of aryl ketones. This two-step transformation is a general method for the acylation of diazonium salts.

Indium(III)-Catalyzed Haloalkynylation Reaction of Alkynes.

Green chemistry strives for sustainability at the molecular level and is gaining increasing relevance in the development of chemical reactions. The haloalkynylation reaction is a highly atom-economical C-C coupling reaction that was previously only achieved using transition metal catalysts. It enables the introduction of an alkyne unit and a halogen atom into the target molecule. Herein, we present a haloalkynylation reaction catalyzed by indium(III) halides. The use of indium(III) bromide as a catalyst leads exclusively to the cis addition products with yields up to 86 %. In addition, iodoacetylenes can be applied for the first time for the haloalkynylation reaction of internal alkynes which is an important step forward in the development of industrially relevant and sustainable catalysts. In contrast to gold catalysis, which proceeds via a similar mechanism, the use of alkyl-substituted haloacetylenes as reagents is also possible. Based on 13C labeling experiments and quantum chemical calculations, we postulate two possible mechanisms for the indium(III)-catalyzed haloalkynylation reactions.

Synthesis of Unsymmetrical Diaryl Tellurides Under Mechanical Ball Milling in Room Temperature

Abstract: An efficient transition metal catalyst-free protocol for the synthesis of unsymmetrical diaryl tellurides has been developed by the reaction of diaryl tellurides and aryl diazonium tetrafluoroborates under mechanical ball milling in the absence of any solvent and base under room temperature. InBr (Indium Bromide) plays an important role in generating the organotelluride nucleophile via the Te-Te bond cleavage of ditelluride. A library of diaryl tellurides bearing both electron-donating and withdrawing groups in the aromatic ring has been synthesized in good to excellent yields by this protocol. Despite very high synthetic importance of diaryl tellurides in the field of organic synthesis, very few protocols have been reported to date for their synthesis. The reactions were also performed on a gram scale without any considerable change in the yields, which surely broadened the applicability of this methodology in the industrial field.

Supramolecular-Interactions-Modulated Photoluminescence in Indium Bromide-Based Isomers.

Here, two isomeric ionic zero-dimensional indium bromide crystals of α (1)/β (2)-[OPy][InBr4(Phen)] (OPy = N-octylpyridinium; Phen = 1,10-phenanthroline) have been isolated simply by changing the cooling conditions in solvothermal syntheses. Structural comparisons indicate their different supramolecular interactions, which can be confirmed by Hirshfeld surface analyses. The crystal 2 has additional hydrogen bonds and π-π interactions; as a result, the more compact stacking of 2 could result in a 10-fold higher photoluminescence (PL) quantum yield (PLQY) than that of 1. Density functional theory calculations confirm the electron transition from the inorganic moiety to the organic ligand, which provides a further understanding of the optical process. This work provides a new idea for designing PL indium-based halides by understanding the structure-PL relationship.

High-Efficiency Intrinsic Yellow-Orange Emission in Hybrid Indium Bromide with Double Octahedral Configuration

Zero-dimensional (0D) In-based organic-inorganic metal halides (OIMHs) have received growing interest in recent years as promising luminescent materials. However, the high efficiencies of 0D In-based OIMHs are all dependent on Sb doping in the existing literature. Here, we report a novel 0D In-based OIMH (C10H22N2)2In2Br10, which exhibits intrinsic broadband emission (610 nm), and the photoluminescence quantum yield (PLQY) can reach 70% without Sb doping. (C10H22N2)2In2Br10 shows a typical 0D structure with three different In-Br polyhedra (two octahedra and one tetrahedron) separated by large organic cations. Based on the optical property measurements and theoretical calculations, we demonstrate that (C10H22N2)2In2Br10 is an indirect semiconductor with a band gap of 3.74 eV, and the In-Br inorganic moiety is primarily responsible for the intense emission of (C10H22N2)2In2Br10. Interestingly, the unique double octahedral configuration in (C10H22N2)2In2Br10 may enhance the structural distortion and stimulate the self-trapped excitons (STEs), leading to the related high PLQY. Our work provides a novel 0D In-based OIMH with high-efficiency intrinsic emission, which is helpful for understanding the structure-PL relationships of hybrid halides.

Methoxyl-substituted phosphine ligand properties and a case study of formation adducts to indium(III) bromide by DFT calculations

Six bulky triphenylphosphine ligands containing substituted methoxyl groups (tris(2,4,6-trimethoxyphenyl)phosphine (TMP), tris(2,6-dimethoxyphenyl)phosphine (TDP), tris(o-methoxyphenyl)phosphine (o-Anis3P), tris(p-methoxyphenyl)phosphine (p-Anis3P), tris(m-methoxyphenyl)phosphine (m-Anis3P) and triphenylphosphine (PPh3)) were studied by DFT (density functional theory) calculations and experimental solution/solid-state 31P NMR spectroscopy. The basicity and binding ability of these substituted ligands, proven by comparison of structural data with DFT-predicted data, are in the order TMP > TDP > o-Anis3P > p-Anis3P > m-Anis3P > PPh3. Molecular structures for InBr3 with bulky ligands (TMP, TDP, o-Anis3P, p-Anis3P, m-Anis3P and PPh3) were calculated using DFT. P-In bond distances generated from these six optimized molecular structures and the calculated intramolecular interaction energies are in agreement with the ligand properties, with strong donation ability for those with the short bond distance; the In-P bond distance from shortest to longest follows a similar trend as predicted by DFT calculations. DFT calculations for these adducts show that methoxyl substitution to triphenylphosphine (PPh3) ligands contributed to its electron donor ability resulting in lower P-In bond distances with relatively large bond interaction energies.

Indium(III) bromide-mediated β-selective thioglycosylation of 1,2,4-O-orthoacetylglucose derivatives

1,2,4-O-Orthoacetyl-α-d-glucose possesses a skew-boat glucopyranose ring whose steric strain is expected to show high reactivity. This study describes the β-selective thioglycosylation of 1,2,4-O-orthoacetyl-α-d-glucose. Indium(III) bromide catalyzes the reaction in trifluoromethylbenzene at ambient temperature in the presence of molecular sieves 4A, resulting in the corresponding thioglycoside product with perfect β-selectivity and high yields. The presented glycosylation might be useful for the synthesis of functional molecules and natural products possessing sugar moieties.

Methoxyl-Substituted Phosphine Ligand Properties and a Case Study of Formation Adducts to Indium(Iii) Bromide by Dft Calculations

Methoxyl-Substituted Phosphine Ligand Properties and a Case Study of Formation Adducts to Indium(Iii) Bromide by Dft Calculations

Synthesis and Physicochemical Properties of Low Viscosity 2‐Ethylhexyl Alkyl Ethers Made from Palm‐Based Esters as Potential Biolubricant

AbstractA series of 2‐ethylhexyl alkyl ethers (EHAE) are synthesized from palm‐based esters via a one‐step reaction under mild reaction conditions for potential usage as biolubricant. In this work, 2‐ethylhexyl esters with varying fatty acid chain lengths are reacted with 1,1,3,3‐tetramethyldisiloxane (TMDS), catalyzed by indium bromide (InBr3) at 40 °C to afford EHAE with lauryl, palmityl, stearyl, and oleyl alkyl chain with 55–68% isolated yield. These compounds are characterized using Fourier‐transform infrared (FTIR) and NMR spectroscopic methods and are evaluated for their viscosity, thermal, cold‐flow, oxidative, and anti‐wear properties. The synthesized EHAEs demonstrate low viscosity (1.65–2.55 cSt at 100 °C) with excellent viscosity indices (130–182). These EHAEs show comparable wear scar diameter (0.6–1.0 mm) in comparison with commercial mineral oil base stock (group I SN150) in the four‐ball wear test. Thermal‐oxidative investigation of the EHAE reveals that the thermal degradation temperatures are in the range of 200–250 °C and oxidation onset temperatures are between 165 and 184 °C. Among the EHAEs, 2‐ethylhexyl lauryl ether with the shortest alkyl chain has the lowest pour point of −27 °C. The physicochemical properties of synthesized EHAEs indicate that they are potential as biolubricant base stocks.Practical Applications: The EHAEs produced from this work exhibit promising physicochemical and lubricity properties, which offer great potential to be used as lubricant base stock especially for internal engine oil application.

Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals.

Identifying plastics capable of chemical recycling to monomer (CRM) is the foremost challenge in creating a sustainable circular plastic economy. Polyacetals are promising candidates for CRM but lack useful tensile strengths owing to the low molecular weights produced using current uncontrolled cationic ring-opening polymerization (CROP) methods. Here, we present reversible-deactivation CROP of cyclic acetals using a commercial halomethyl ether initiator and an indium(III) bromide catalyst. Using this method, we synthesize poly(1,3-dioxolane) (PDXL), which demonstrates tensile strength comparable to some commodity polyolefins. Depolymerization of PDXL using strong acid catalysts returns monomer in near-quantitative yield and even proceeds from a commodity plastic waste mixture. Our efficient polymerization method affords a tough thermoplastic that can undergo selective depolymerization to monomer.

Analysis of Post-Deposition Recrystallization Processing via Indium Bromide of Cu(In,Ga)Se2 Thin Films.

Cu(In,Ga)Se2 (CIGS) thin films were deposited at low temperature (350 °C) and high rate (10 µm/h) by a single stage process. The effect of post-deposition treatments at 400 °C and 500 °C by indium bromide vapor were studied and compared to the effect of a simple annealing under selenium. Structural, electrical, and chemical analyses demonstrate that there is a drastic difference between the different types of annealing, with the ones under indium bromide leading to much larger grains and higher conductivity. These properties are associated with a modification of the elemental profiles, specifically for gallium and sodium.

Zero-Dimensional Hybrid Organic-Inorganic Indium Bromide with Blue Emission.

Low-dimensional hybrid organic-inorganic metal halides have received increased attention because of their outstanding optical and electronic properties. However, the most studied hybrid compounds contain lead and have long-term stability issues, which must be addressed for their use in practical applications. Here, we report a new zero-dimensional hybrid organic-inorganic halide, RInBr4, featuring photoemissive trimethyl(4-stilbenyl)methylammonium (R+) cations and nonemissive InBr4- tetrahedral anions. The crystal structure of RInBr4 is composed of alternating layers of inorganic anions and organic cations along the crystallographic a axis. The resultant hybrid demonstrates bright-blue emission with Commission Internationale de l'Eclairage color coordinates of (0.19, 0.20) and a high photoluminescence quantum yield (PLQY) of 16.36% at room temperature, a 2-fold increase compared to the PLQY of 8.15% measured for the precursor organic salt RBr. On the basis of our optical spectroscopy and computational work, the organic component is responsible for the observed blue emission of the hybrid material. In addition to the enhanced light emission efficiency, the novel hybrid indium bromide demonstrates significantly improved environmental stability. These findings may pave the way for the consideration of hybrid organic In(III) halides for light emission applications.

Азозамещенные этоксиакридина – реагент для экстракционно-фотометрического определения индия(III)

The associates of bromo-indate with azo-substituted ethoxyacridine have been studied by spectrophoto-metric method. It has been found that the associates are well extracted with a mixture of chloroform acetone (4:1). The optimum volume of aqueous and organic phase is equal to 5 ml. The molar ratio of the components in the extractable compounds was studied by the methods of isomolar series, equilibrium shift and a straight line. It was found that bromo-indate associated with azo-ethoxyacridines (AE) in a ratio of 1:1. Study of the effect of foreign ions on the accuracy of the determination of indium with azo-substituted ethoxyacridine showed that the number of ions does not interfere (in parentheses are multiple relationships to indium ions); CdII (1200), NH4+ (4000), Zn2+ (1500), CoII (1100), NiII (1050), CuII (500), FeII (4000), PbII (250), Nb (250), TaV (270), Al3+ (2000), ReVII (140), B3+ (410), C2O42- (1900), CH3COO- (1300), ascorbic acid (270), citrate ion (3500), tartrates (4000), EDTA (3700). Number of ions interfered the determination: TlIII (1), FeIII (1), Ga3+ (1), HgII (1), SbV (1), AuIII (1), thiourea (4). It was studied formation and extraction of associates of bromo-indate with AEADPA (2-ethoxy-6-(4-N,N-dipropylphenylazo)-9-aminoacridine) and AEADEA (2-ethoxy-6-(N,N-ethylphenylazo)-9-aminoacridine). The maxima of light absorption of bromo-indate with AEADPA is observed at 530 nm, and the AEADEA at 515 nm. The physico-chemical and analytical characteristics of the azo-substituted ethoxyacridines and their ionic associates with indium bromide acid complexes (λmax ε, βkD, D, R%) were determined. It was shown that bromo-indate compounds with azo-substituted ethoxyacridines are ionic associates, the molar ratios of the components in which are: [İn III] : [Br -] : R + = 1:4:1. Highly efficient extraction-photometric methods have been developed for the determination of trace amounts of indium in various objects.

Lithium-Ion Transport in Nanocrystalline Spinel-Type Li[InxLiy]Br4 as Seen by Conductivity Spectroscopy and NMR.

Currently, a variety of solid Li+ conductors are being discussed that could potentially serve as electrolytes in all-solid-state Li-ion batteries and batteries using metallic Li as the anode. Besides oxides, sulfides and thioposphates, and also halogenides, such as Li3YBr6, belong to the group of such promising materials. Here, we report on the mechanosynthesis of ternary, nanocrystalline (defect-rich) Li[InxLiy]Br4, which crystallizes with a spinel structure. We took advantage of a soft mechanochemical synthesis route that overcomes the limitations of classical solid-state routes, which usually require high temperatures to prepare the product. X-ray powder diffraction, combined with Rietveld analysis, was used to collect initial information about the crystal structure; it turned out that the lithium indium bromide prepared adopts cubic symmetry (). The overall and electronic conductivity were examined via broadband conductivity spectroscopy and electrical polarization measurements. While electric modulus spectroscopy yielded information on long-range ion transport, 7Li nuclear magnetic resonance (NMR) spin-lattice relaxation measurements revealed rapid, localized ionic hopping processes in the ternary bromide. Finally, we studied the influence of thermal treatment on overall conductivity, as the indium bromide might find applications in cells that are operated at high temperatures (330 K and above).

Application of plasma lighting for growth and flowering of tomato plants

Plasma lighting systems have been engineered to simulate sunlight. The objective of this study was to determine the effects of plasma lighting on tomato plant growth, photosynthetic characteristics, flowering rate, and physiological disorders. Tomato plants were grown in growth chambers at air temperatures of 25/23 °C (light/dark period), in a 16 h day−1 light period provided by four different light sources: 1 kW and 700 W sulfur plasma lights (1 SPL and 0.7 SPL), 1 kW indium bromide plasma light, and 700 W high pressure sodium lamp (0.7 HPS) as a control. The total dry weight and leaf area at 0.7 SPL were approximately 1.2 and 1.3 times greater, respectively, than that of 0.7 HPS at the 62 days after sowing (DAS). The maximum light assimilation rate was observed at 1 SPL at the 73 DAS. In addition, the light compensation and saturation points of the plants treated with plasma lighting were 98.5% higher compared with HPS. Those differences appeared to be related to more efficient light interception, provided by the SPL spectrum. The percentage of flowering at 0.7 SPL was 30.5%, which was higher than that at 0.7 HPS; however, there were some instances of severe blossom end rot. Results indicate that plasma lighting promotes tomato growth, flowering, and photosynthesis. Therefore, a plasma lighting system may be a valuable supplemental light source in a greenhouse or plant factory.

A Five-Component Biginelli-Diels-Alder Cascade Reaction.

A new multi-component condensation was discovered during the reaction of a urea, β-keto ester, and formaldehyde. In the presence of catalytic indium bromide, a Biginelli dihydropyrimidinone intermediate was further converted to a five-component condensation product through a formal hetero Diels-Alder reaction. The product structure was confirmed by NMR and NOE analysis, and the proposed stepwise mechanism was supported by the reaction of the Biginelli intermediate with ethyl 2-methylene-3-oxobutanoate.

Simple and Efficient Preparation of O- and S-GlcNAcylated Amino Acids through InBr3-Catalyzed Synthesis of β- N-Acetylglycosides from Commercially Available Reagents.

The facile synthesis of serine, threonine, and cysteine β-glycosides using commercially available peracetylated β- N-acetylglucosamine (β-Ac4GlcNAc) and catalytic amounts of indium bromide (InBr3) is described. This method involves only inexpensive reagents that require no further modification or special handling. The reagents are simply mixed, dissolved, and refluxed to afford the GlcNAcylated amino acids in great yields (70-80%). This operationally simple procedure should facilitate the study of O-GlcNAcylation without necessitating expertise in synthetic carbohydrate chemistry.

Preparation of Substituted Compounds of Lithium Indium Bromide and Fabrication of All Solid-State Battery

Preparation of Substituted Compounds of Lithium Indium Bromide and Fabrication of All Solid-State Battery

Synthesis of Novel Diverse Methoxybenzenes‐substituted 2H/4H‐chromene Derivatives in the Presence of InBr3 (5 mol%) and their Cytotoxic Activity

A series of novel 2‐(trifluoromethyl)‐2H/4H‐chromene‐3‐carboxylate isomers 3 and 4 functionalized with diverse methoxybenzenes 2 at position 4 in compound 3 and position 2 in compound 4 were prepared in different proportions by nucleophilic substitution on ethyl 2‐hydroxy‐2‐(trifluoromethyl)‐2H‐chromene‐3‐carboxylate 1 in single step promoted by Indium (III) bromide (5 mol%) a Lewis acid. Regiospecific isomers 3k, 3l, 3m, and 3n prepared by using sterically bulk 1,3,5‐trimethoxy benzene substrate 2e in this reaction. Further, isomers 3a and 4a independently on reaction with amines, only compound 3a could give Michael addition products 5a–c. All the compounds 3a–n, 4a–j, and 5a–c were screened for cytotoxic activity against four human cancer cell lines and found to show high activity at micromolar concentration. The compounds 4h and 5a–c showed promising cytotoxic activity against the tested cancer cell lines. Further, these compounds 4h and 5a–c were docked with protein (1SA0) on colchicine‐binding site of β tubulin suggesting that tubulin inhibition could be the possible mechanism of action for these compounds.

ChemInform Abstract: Oxidative Coupling of Terminal Alkynes with Aldehydes Leading to Alkynyl Ketones by Using Indium(III) Bromide.

AbstractThe straightforward access to ynones proceeds trough nucleophilic addition and Oppenauer oxidation mediated by stoichiometric amounts of indium tribromide.