Iodine Monobromide Research Articles

An Alkyne-Bridged Covalent Organic Framework Featuring Interactive Pockets for Bromine Capture.

The high degree of corrosivity and reactivity of bromine, which is released from various sources, poses a serious threat to the environment. Moreover, its coexistence with iodine forming an equilibrium compound, iodine monobromide (IBr) necessitates the selective capture of bromine from halogen mixtures. The electrophilicity of halogens to π-electron rich structures enabled us to strategically design a covalent organic framework for halogen capture, featuring a defined pore environment with localized sorption sites. The higher capture capacity of bromine (4.6 g g-1) over iodine by ~41 % shows its potential in selective capture. Spectroscopic results uncovering the preferential interaction sites are supported by theoretical investigations. The alkyne bridge is a core functionality promoting the selectivity in capture by synergistic physisorption, rationalized by the higher orbital overlap of bromine due to its smaller atomic size as well as reversible chemical interactions. The slip stacking in the structure has further promoted this phenomenon by creating clusters of molecular interaction sites with bromine intercalated between the layers. The inclusion of unsaturated moieties, i.e. triple bonds and the complementary pore geometry offer a promising design strategy for the construction of porous materials for halogen capture.

Eine Alkin‐verbrückte kovalent organische Gerüstverbindung mit interaktiven Bindungstaschen für das Einfangen von Brom

AbstractDie hohe Korrosivität und Reaktivität von Brom, welches aus verschiedenen Quellen freigesetzt wird, stellt eine ernsthafte Gefahr für die Umwelt dar. Darüber hinaus erfordert seine Koexistenz mit Iod und die daraus resultierende Gleichgewichtsverbindung Iodmonobromid (IBr) die selektive Abtrennung von Brom aus Halogengemischen. Die Elektrophilie von Halogenen gegenüber π‐elektronenreichen Strukturen ermöglichte uns die strategische Entwicklung einer kovalent organischen Gerüstverbindung für die Halogenaufnahme, die eine definierte Porenumgebung mit lokalisierten Sorptionsstellen aufweist. Die um ~41 % höhere Aufnahmekapazität von Brom (4,6 g g−1) gegenüber Iod zeigt das Potenzial für die selektive Aufnahme. Die spektroskopischen Ergebnisse, welche die bevorzugten Wechselwirkungsstellen aufzeigen, werden durch theoretische Untersuchungen gestützt. Die Alkin‐Brücke ist eine Kernfunktionalität, die die Selektivität bei der Aufnahme durch synergistische Physisorption fördert, was durch die höhere Orbitalüberlappung von Brom aufgrund seiner geringeren atomaren Größe, sowie durch reversible chemische Wechselwirkungen begründet ist. Das sogenannte „slip stacking“ in der Struktur hat dieses Phänomen weiter gefördert, indem Cluster molekularer Interaktionsstellen mit zwischen den Schichten eingelagertem Brom geschaffen wurden. Die Einführung ungesättigter Einheiten, d. h. Dreifachbindungen, und die komplementäre Porengeometrie bieten eine vielversprechende Designstrategie für die Konstruktion poröser Materialien für die Halogenaufnahme.

Kut D., Kut M., Onysko M., Lendel V. STUDY OF REGIO- AND STEREO-SELECTIVITY OF HALOGEN-INDUCED CYCLIZATION OF TERMINAL PROPARGYL THIOETHERS OF 3-ALKYL(PHENYL)QUINAZOLINE-4-ONES

Polycyclic condensed quinazoline derivatives are biologically valuable compounds that have found their application in pharmaceutical and medicinal chemistry. Their practical use makes such compounds interesting and promising, and their synthesis is an urgent task. In the present work, the regio- and stereo-selectivity of the halocyclic reaction of propargyl thioethers of 2-thioxoquinazoline-4-one with bromine, iodine and iodine bromide, the effect of solvent polarity, acceptor substituent at position 7 of quinazoline, and the steric effect of the substituent at N(3) of quinazoline on the course of the electrophilic heterocyclic reaction were investigated. It was found that the halogenation of 3-alkyl-2-thioxo-2,3-dihydroquinazoline-4(1H)-ones in chloroform or ice-cold acetic acid proceeds regio- and stereo-selectively with the formation of salt-like thiazoloquinazoline halides. On the contrary, the stereoselectivity of halogenation of the 3-phenyl substituted propargyl thioether of quinazoline depends on the polarity of the solvent and in chloroform leads to the formation of a mixture of configurational isomers of thiazoloquinazoline tribromide, while in acetic acid, presumably, one geometric isomer is formed. The structure of the obtained polycyclic systems was proved on the basis of NMR spectroscopy and elemental analysis.
 Keywords: propargyl thioethers; halogenation; stereo-selectivity; regio-selectivity; thiazoloquinazoline halides.

Regio- and stereo-selective halogen-induced cyclization of terminal alkynyl thioethers of 3-phenylquinazoline-4-one

The present work reports the results of the study of the electrophilic heterocyclization of terminal alkynyl thioethers of quinazoline-4-one under the action of halogens. Starting 2-(but-3-in-1-ylthio)-3-phenylquinazolin-4(3H)-one and 2-(pent-4-in-1-ylthio)-3-phenylquinazolin-4(3H)-one were prepared by alkylation of 2-thioxoquinazolin-4-one with butynyl and pentynyl bromide in an alcoholic-alkaline medium, respectively. It was determined that the interaction of 2-(but-3-in-1-ylthio)-3-phenylquinazoline-4(3H)-one with bromine, iodine and iodine bromide is regio- and stereo-selective and leads to the formation of 1-(halogenomethylidene)-6-oxo-5-phenyl-2,3,5,6-tetrahydro-1H-[1,3]thiazino[3,2-a]quinazolinium halides of angular structure as E-isomers. On the contrary, the halogen-induced heterocyclization of 2-(pent-4-in-1-ylthio)-3-phenylquinazolin-4(3H)-one leads to the annelation of thiazepine cycle to quinazoline core with formation of E-1-(bromomethylidene)-7-oxo-6-phenyl-1,2,3,4,6,7-hexahydro-[1,3]thiazepino[3,2-a]quinazolinium tribromide and E-1-(iodomethylidene)-7-oxo-6-phenyl-1,2,3,4,6,7-hexahydro-[1,3]thiazepino[3,2-a]quinazolinium monobromide. It was found that an increase in the carbon length of the terminal alkynyl substituent by one methylene group affects the regioselectivity of the halocyclization process, but does not affect the stereoselectivity.

Synthesis and conversion of thiazinobenzothiazolium salts

This paper presents the results of research into the process of electrophilic intramolecular cyclization of 2-cinnamylthiobenzothiazole with halogens and tellurium halides. 2-Cinnamylthiobenzothiazole was prepared by alkylation of mercaptobenzothiazole with cinnamyl chloride in the presence of sodium alcoholate in an alcoholic medium. It was established that as a result of halocyclization of the model 2-cinnamylthiobenzothiazole with an excess of halogen, the thiazine ring is annealed with the formation of 3-halogeno-4-phenyl-3,4-dihydro-2H-[1,3]thiazino[2,3-b][1,3 ]benzothiazolium tribromide trihalides, which are effectively dehalogenated with acetone or sodium sulfite to form monohalides. Halocyclization of cinnamyl thioether of benzothiazole with iodine bromide in chloroform isolated 3-iodo-4-phenyl-3,4-dihydro-2H-[1,3]thiazino[2,3-b][1,3]benzothiazolium bromide, which was converted into 3-iodo-4-phenyl-3,4-dihydro-2H-[1,3]thiazino[2,3-b][1,3]benzothiazolium iodide by ion exchange reaction under the action of potassium iodide in acetone. The corresponding perchlorate was synthesized by the action of sodium perchlorate in methanol on 3-bromo-4-phenyl-3,4-dihydro-2H-[1,3]thiazino[2,3-b][1,3]benzothiazolium bromide. Spectral characteristics (1H NMR) of trihalides, monohalides and perchlorate indicate the preservation of the structure of the thiazinobenzothiazolium cation during ion exchange reactions. Tellurium-induced cyclization of cinnamyl thioether of benzothiazole does not occur. When 2-cinnamylthiobenzothiazole is treated with tellurium dioxide in an excess of halide acid, the nitrogen of the benzothiazole cycle is protonated and aquacomplexes of benzothiazolinium hexahalogenotellurates are formed. Instead, the action of p-alkoxyphenyltellurttrichloride on cinnamyl thioether benzothiazole leads to the formation of molecular complexes in the ratio of thioether:electrophile of 2:1. As a result of the conducted research, potentially biologically active thiazinobenzothiazolium halides were synthesized.

Role of Iodine Recycling on Sea-Salt Aerosols in the Global Marine Boundary Layer.

Heterogeneous uptake of hypoiodous acid (HOI), the dominant inorganic iodine species in the marine boundary layer (MBL), on sea‐salt aerosol (SSA) to form iodine monobromide and iodine monochloride has been adopted in models with assumed efficiency. Recently, field measurements have reported a much faster rate of this recycling process than previously assumed in models. Here, we conduct global model simulations to quantify the range of effects of iodine recycling within the MBL, using Conventional, Updated, and Upper‐limit coefficients. When considering the Updated coefficient, iodine recycling significantly enhances gaseous inorganic iodine abundance (∼40%), increases halogen atom production rates (∼40% in I, >100% in Br, and ∼60% in Cl), and reduces oxidant levels (−7% in O3, −2% in OH, and −4% in HO2) compared to the simulation without the process. We appeal for further direct measurements of iodine species, laboratory experiments on the controlling factors, and multiscale simulations of iodine heterogeneous recycling.

Synthesis, Structure, and UV-Vis Characterization of Antimony(III) Phthalocyanine: [(SbPc)2(Sb2I8)(SbBr3)]2.

A new antimony(III)–phthalocyanine complex with the formula of [(SbPc)2(Sb2I8)(SbBr3)]2 has been obtained in the reaction of pure antimony powder with phthalonitrile under the oxidation conditions by iodine monobromide vapors. The complex crystallizes in the centrosymmetric space group of the triclinic system. Both independent (SbPc)+ units exhibit non-planar conformation, since the Sb(III) is larger than the equilibrium cavity size of the ring and cannot be accommodated without its expansion; thus, the metal protrudes out of the cavity, forming a saucer shape. The centrosymmetric anionic unit of the crystal consists of two (Sb2I8)2− interacted anionic units forming (Sb4I16)4− anionic complex that interacts with two SbBr3 molecules to form [Sb6I16Br6]4− anionic aggregate. Each [Sb6I16Br6]4− anionic aggregate is surrounded by four (SbPc)+ cations forming a supramolecular centrosymmetric (SbPc)4[Sb6I16Br6] complex. Translationally related (SbPc)4[Sb6I16Br6] molecules form a stacking structure along the [100] and [011] directions with N4–N4 distances of 3.55 and 3.53 Å, respectively, between the back-to-back-oriented saucer-shaped (SbPc)+ units. The interaction between the building units of the crystal was analyzed using the Hirshfeld surface and the analysis of the 2D fingerprint plots. The UV–Vis absorption spectra of crystal 1 were taken in CH2Cl2 and toluene solutions in the concentration range from 10−5 to 10−6 mol/L. No significant changes related to aggregation in solutions were observed. The Q-band in toluene solution is red shifted by ~15 nm in comparison to that in CH2Cl2 solution. Oxidation of (SbPc)4[Sb6I16Br6] yields SbVPc derivative. Both SbIII and SbV phthalocyanine derivatives absorb near infrared light (600–900 nm), which should be intriguing from the point of view of potential use as photosensitizers for PDT and as an infrared cut filter for plasma display and silicon photodiodes.

Significance of the cronobiological factors in a spa treatment of gynaecological patients

In the article the outcomes of the research of efficiency of complex SPA treatment of the patients with chronic inflammatory diseases of organs of the small pelvis in various seasons of the year in conditions of humid subtropics are indicated. The dynamics ofa psycho-emotional condition, vegetative reactivity, condition of the protective-adapting mechanisms of the gomeostasis are investigated, depending on a kind of applied SPA treatment (hydrogen sulfide or iodine bromide)? In cool and warm periods of a year. The recommendations for differentiated rehabilitation treatment of patients with valiants of clinical process of chronic inflammatory diseases of organs of the small pelvis and complications, accompanying them, in conditions of humid subtropics are represented.

Lead-Dominated Hyperfine Interaction Impacting the Carrier Spin Dynamics in Halide Perovskites.

The outstanding optical quality of lead halide perovskites inspires studies of their potential for the optical control of carrier spins as pursued in other materials. Entering largely uncharted territory, time-resolved pump-probe Kerr rotation is used to explore the coherent spin dynamics of electrons and holes in bulk formamidinium caesium lead iodine bromide (FA0.9 Cs0.1 PbI2.8 Br0.2 ) and to determine key parameters characterizing interactions of their spins, such as the g-factors and relaxation times. The demonstrated long spin dynamics and narrow g-factor distribution prove the perovskites as promising competitors for conventional semiconductors in spintronics. The dynamic nuclear polarization via spin-oriented holes is realized and the identification of the lead (207 Pb) isotope in optically detected nuclear magnetic resonance proves that the hole-nuclei interaction is dominated by the lead ions. A detailed theoretical analysis accounting for the specifics of the lead halide perovskite materials allows the evaluation of the underlying hyperfine interaction constants, both for electrons and holes. Recombination and spin dynamics evidence that at low temperatures, photogenerated electrons and holes are localized at different regions of the perovskite crystal, resulting in their long lifetimes up to 44μs. The findings form the base for the tailored development of spin-optoelectronic applications for the large family of lead halide perovskites and theirnanostructures.

Thermoelectric power of graphite intercalation compounds with iodine monobromide

Thermoelectric power of graphite intercalation compounds with iodine monobromide

A “nucleophilic” iodine in a halogen-bonded iodonium complex manifests an unprecedented I+···Ag+ interaction

Summary When an electron is removed from a halogen atom, it forms a halenium ion X+ (X = I, Br, Cl). In halogen bonding (XB), X+ is considered as a strong XB donor, and when interacting with two XB acceptors (e.g., pyridine), it forms a halonium XB complex with a [N–I–N] three-center-four-electron bond with the two XB acceptors. An unprecedented I+···Ag+ interaction occurs between a [L1–I–L1]+ halogen-bonded complex and a [L2–Ag–L2]+ complex in which the iodonium ion acts like a nucleophile and donates electrons to the silver(I) cation. The X-ray diffraction analysis reveals a short contact [3.4608(3) A] between the I+ and Ag+ cations, and ITC measurements give a ΔG of −6.321 kcal/mol and Ka∼37,000 M−1 for the 1:1 complex. The DFT computational study on the nature of the I+···Ag+ interaction indicates that the I+ is nucleophilic in character, manifesting an unusual and strongly attractive interaction between the I+ and Ag+ cations.

Direct field evidence of autocatalytic iodine release from atmospheric aerosol

Reactive iodine plays a key role in determining the oxidation capacity, or cleansing capacity, of the atmosphere in addition to being implicated in the formation of new particles in the marine boundary layer. The postulation that heterogeneous cycling of reactive iodine on aerosols may significantly influence the lifetime of ozone in the troposphere not only remains poorly understood but also heretofore has never been observed or quantified in the field. Here, we report direct ambient observations of hypoiodous acid (HOI) and heterogeneous recycling of interhalogen product species (i.e., iodine monochloride [ICl] and iodine monobromide [IBr]) in a midlatitude coastal environment. Significant levels of ICl and IBr with mean daily maxima of 4.3 and 3.0 parts per trillion by volume (1-min average), respectively, have been observed throughout the campaign. We show that the heterogeneous reaction of HOI on marine aerosol and subsequent production of iodine interhalogens are much faster than previously thought. These results indicate that the fast formation of iodine interhalogens, together with their rapid photolysis, results in more efficient recycling of atomic iodine than currently considered in models. Photolysis of the observed ICl and IBr leads to a 32% increase in the daytime average of atomic iodine production rate, thereby enhancing the average daytime iodine-catalyzed ozone loss rate by 10 to 20%. Our findings provide direct field evidence that the autocatalytic mechanism of iodine release from marine aerosol is important in the atmosphere and can have significant impacts on atmospheric oxidation capacity.

Polycentric binding in complexes of trimethylamine-N-oxide with dihalogens.

Dihalogens readily interact with trimethylamine-N-oxide under ambient conditions. Accordingly, herein, stable 1 : 1 adducts were obtained in the case of iodine chloride and iodine bromide. The crystal and molecular structure of the trimethylamine-N-oxide–iodine chloride adduct was solved. Furthermore, the geometry and electronic structure of the trimethylamine-N-oxide–dihalogen complexes were studied computationally. Only molecular ensembles were found in the global minimum for the 1 : 1 stoichiometry. The O⋯X–Y halogen bond is the main factor for the thermodynamic stability of these complexes. Arguments for electrostatic interactions as the driving force for this noncovalent interaction were discussed. Also, the equilibrium structures are additionally stabilised by weak C–H⋯X hydrogen bonds. Consequently, formally monodentate ligands are bound in a polycentric manner.

Optical properties of alkali halide crystals

The results of measuring the transparency bands in a wide wavelength range - from UV to 3000 μm for crystals of sodium chloride (NaCl), potassium chloride (KCl), iodine bromide (KBr) and rubidium iodide (RbI) are presented. It was shown that, along with well-known data on the transparency of these crystals in the UV and IR ranges, they have a transmission zone in the THz range in the region of 1000 μm.

Electrophilic ipso-Halocyclization of N-Phenyl-N-triflylpropiolamides Leading to 8-Halo-1-azaspiro[4.5]deca-3,6,9-trien-2-ones

N-Phenyl-N-triflylpropiolamides react with iodine chloride or iodine bromide by an intramolecular electrophilic ipso-halocyclization/nucleophilic halide addition sequence to furnish cyclohexadiene-spiro-γ-lactams. These products can undergo cleavage of the amide bond with primary amines and of the N–Cspiro bond with secondary amines, leading to N-alkyl-2-iodo-3-phenylacrylamides and N-(4-halophenyl)-2-iodo-3-(2-triflylamino)phenylacrylamides, respectively.

Mediator Catalyst for Lithium Fluoride Decomposition for Lithium Recovery

A catalyst to electrochemically decompose lithium fluoride (LiF), which is abound in the electrode of the spent LiBs, was studied to develop a Li reproduction technology. Since the oxidizing activity of halogen I₂, Br₂, Cl₂, or F₂, increases, the reaction I₂ + 2LiF → F₂ + 2LiI cannot proceed. We examined the catalytic activity of interhalogens such as iodine monobromide (IBr) and iodine chloride (ICl) for LiF decomposition in specific organic solvents. We observed the chemical decomposition of LiF in IBr and ICl dimethyl sulfoxide (DMSO) solutions. This decomposition was induced by an increase in solution acidity, accompanied by a large deviation in the electric charge between two halogen elements due to the complex formation of interhalogen with DMSO. A double-chamber-type cell for Li recovery from LiF was constructed by combining this LiF decomposition behavior with redox coupling of IBr or ICl operated by electrical charging. The cell was first demonstrated to be chargeable due to the continuous decomposition of LiF.

Iodine Value in Partially Hydrogenated Castor Oil (Ricinus Oil) as determined by AOCS Official Method Cd 1-25 (Wijs’ Method)

The Iodine Value (Iodine Number) is an important analytical characteristic of fats and oils. The iodine (I2 ) required saturating the fatty acids present in 100 grams of the oil or fat. Iodine is essential element of human nutrition. A third of the global population has insufficient iodine intake and is at risk of developing Iodine Deficiency Disorder. Oils rich in saturated fatty acids have low iodine value, while oils rich in unsaturated fatty acids (α- linoleic acid) have high iodine value. Several variations of iodine value have been developed, although Iodine Monobromide Method or Hanus Metod, Iodine Monochloride Method or Wijs’ Method, and Pyridine Bromide Method or Iodine-Mercuric Chloride in alcohol (Hubl). The based on American Oil Chemists’ Society (AOCS) Cd 1-25 describes the determination of the iodine value (a measure of unsaturation) in Partially Hydrogenated Castor Oil (COH); the specification is 28-32 g I2 /100 g sample.

Potentiometric Sensor For Analgin Determination In Pharmaceutical Formulations

Ion associates (IA) of butylrodamine C with triiodide and iod bromide have been synthesized. Their thermal behavior is investigated. Thermolysis synthesized by IA BR+I3¯ passes through a number of intermediate stages, since the C4H9 radical, which is part of the dye, has a significant effect on the process of thermolysis of the ionic associate. IA BR+I3¯ begins to decompose significantly at a temperature higher than 140 єC with an endothermic effect at 240 єC and two small exothermic effects with a maximum at 282 єC and 355 єC (corresponding to the release of 2NH3, 8C2H4, 2HI). In the range of 380–720 єC, the exothermic effect of the IA combustion occurs at a temperature of 485 єC with significant mass loss. The obtained IAs are stable under normal conditions. An I3¯ and I2Br¯ sensor containing butyrodromine C associate of butylrodamine C with triiodide and iodum bromide was developed. The working interval of the pH of the triiodide sensor is 2 - 12, and for iodum bromide, the pH is 2 - 10, respectively. The linearity interval of the electrode function is in the range 9 ∙10-6 - 1 ∙10-1 mol L-1, the slope is 65 mV/pC for the triiodide, and for the iodine bromide - 1 ∙10-5 - 1 ∙10-1 mol L-1, the slope 68 mV/pC. The technique of potentiometric determination of analgin in medicines is developed.

Chemical inhibition of reversible decomposition for efficient and super-stable perovskite solar cells

Despite the remarkable photovoltaic characteristics and printability of perovskite solar cells, their intrinsic instability has been the most serious drawback toward future commercialization. In this work, we have investigated the stability of perovskite films in terms of morphology, electronic properties and chemical compositions. Specifically, the chemical decomposition inhibition strategy was introduced in perovskite films through iodine bromide to modify the crystal defects, leading to PSCs with suppressed hysteresis effects, superior durability and attractive PCE of 21.5%. Femto-second transient absorption spectra and GIWAXS measurements provide deep insight into the reduced carrier recombination and indicate the improved crystallinity of the modified perovskite films. Furthermore, an efficient hole-transporting material, PDPP4T, without using any doping process is applied to achieve PSCs with enhanced open-circuit voltage and better repeatability. As a consequence, the modified PSCs could maintain 82% of their initial efficiency after 5000 h of storage in ambient conditions and 90% of their initial efficiency after 1000 h of light soaking process. An excellent water resistance up to 100 h of the PSCs is also obtained by encapsulation technology. Besides, after coating Ce3+-CsPbI3 nanocrystals as luminescent down-shifting layers on the front side of the PSCs, the PCE of the device was further improved to 22.16%.

Direct mapping of curve-crossing dynamics in IBr by attosecond transient absorption spectroscopy.

The electronic character of photoexcited molecules can abruptly change at avoided crossings and conical intersections. Here, we report direct mapping of the coupled interplay between electrons and nuclei in a prototype molecule, iodine monobromide (IBr), by using attosecond transient absorption spectroscopy. A few-femtosecond visible pulse resonantly excites the [Formula: see text], Y(0+), and Z(0+) states of IBr, and the photodissociation dynamics are tracked with an attosecond extreme-ultraviolet pulse that simultaneously probes the I-4d and Br-3d core-level absorption edges. Direct comparison with quantum mechanical simulations unambiguously identifies the absorption features associated with adiabatic and diabatic channels at the B/Y avoided crossing and concurrent two-photon dissociation processes that involve the Y/Z avoided crossing. The results show clear evidence for rapid switching of valence-electronic character at the avoided crossing.