Tetrabutylammonium iodide-catalyzed oxidative α-azidation of ß-ketocarbonyl compounds using sodium azide.

We herein report the oxidative α-azidation of carbonyl compounds by using NaN3 in the presence of dibenzoyl peroxide catalyzed by tetrabutylammonium iodide (TBAI). By utilizing these readily available bulk chemicals a variety of cyclic ß-ketocarbonyl derivatives can be efficiently α-azidated under operationally simple conditions. Control experiments support a mechanistic scenario involving in situ formation of an ammonium hypoiodite species which first facilitates the α-iodination of the pronucleophile, followed by a phase-transfer-catalyzed nucleophilic substitution by the azide. Furthermore, we also show that an analogous α-nitration by using NaNO2 under otherwise identical conditions is possible as well.

A Radical Activation Strategy for Versatile and Stereoselective N-Glycosylation.

Previous N-glycosylation approaches have predominately involved acidic conditions, facing challenges of low stereoselectivity and limited scope. Herein, we introduce a radical activation strategy that enables versatile and stereoselective N-glycosylation using readily accessible glycosyl sulfinate as a donor under basic conditions and exhibits exceptional tolerance towards various N-aglycones containing alkyl, aryl, heteroaryl and nucleobase functionalities. Preliminary mechanistic studies indicate a pivotal role of iodide, which orchestrates the formation of a glycosyl radical from the glycosyl sulfinate and subsequent generation of the key intermediate, a configurationally well-defined glycosyl iodide, which is subsequently attacked by an N-aglycone in a stereospecific SN2 manner to give the desired N-glycosides. An alternative route involving the coupling of a glycosyl radical and a nitrogen-centered radical is also proposed, affording the exclusive 1,2-trans product. This novel approach promises to broaden the synthetic landscape of N-glycosides, offering a powerful tool for the construction of complex glycosidic structures under mild conditions.

Pressure Induces Six-fold Coordination for the Lighter Pnictides Phosphorus and Arsenic Triiodide.

In this study, we employ an evolutionary algorithm in conjunction with first-principles density functional theory (DFT) calculations to comprehensively investigate the structural transitions, electronic properties, and chemical bonding behaviors of XI3 compounds, where X denotes phosphorus (P) and arsenic (As), across a range of elevated pressures. Our computational analyses reveal a distinctive phenomenon occurring under compression, wherein the initially trigonal structures of PI3 (P 63) and AsI3 (R-3) undergo an intriguing transformation, leading to the emergence of six-coordinated monoclinic phases (C2/m) at 6 GPa and 2 GPa for PI3 and AsI3, respectively. These high-pressure phases exhibit their stability up to 10 GPa for PI3 and 12 GPa for AsI3. Notably, the resulting structures at elevated pressures bear striking resemblance to the widely recognized six-coordinated octahedral BiI3 crystal configuration observed at ambient conditions. Our investigation further underscores the pivotal role of pressure-induced reactivity of the lone-pair electrons in PI3 and AsI3, facilitating their enhanced stereochemical reactivity and thereby enabling higher six-fold coordination. Complementary analyses employing electron localization function (ELF) and density of states (DOS) effectively delineate the progression towards augmented coordination in PI3 and AsI3 with increasing pressure. While the phenomenon of heightened coordination is conventionally associated with heavier pnictide iodides such as SbI3 and BiI3 under ambient conditions due to heightened ionic character and relativistic effects in bismuth (Bi) and antimony (Sb), our findings accentuate that analogous structural transformations can also be induced in lighter elements like phosphorus (P) and arsenic (As) under the influence of pressure.

Third Harmonic Generation in Thin NbOI2 and TaOI2.

The niobium oxide dihalides have recently been identified as a new class of van der Waals materials exhibiting exceptionally large second-order nonlinear optical responses and robust in-plane ferroelectricity. In contrast to second-order nonlinear processes, third-order optical nonlinearities can arise irrespective of whether a crystal lattice is centrosymmetric. Here, we report third harmonic generation (THG) in two-dimensional (2D) transition metal oxide iodides, namely NbOI2 and TaOI2. We observe a comparable THG intensity from both materials. By benchmarking against THG from monolayer WS2, we deduce that the third-order susceptibility is approximately on the same order. THG resonances are revealed at different excitation wavelengths, likely due to enhancement by excitonic states and band edge resonances. The THG intensity increases for material thicknesses up to 30 nm, owing to weak interlayer coupling. After this threshold, it shows saturation or a decrease, due to optical interference effects. Our results establish niobium and tantalum oxide iodides as promising 2D materials for third-order nonlinear optics, with intrinsic in-plane ferroelectricity and thickness-tunable nonlinear efficiency.

Cubic Iodide Lix YI3+x Superionic Conductors through Defect Manipulation for All-Solid-State Li Batteries.

Halide solid electrolytes (SEs) have attracted significant attention due to their competitive ionic conductivity and good electrochemical stability. Among typical halide SEs (chlorides, bromides, and iodides), substantial efforts have been dedicated to chlorides or bromides, with iodide SEs receiving less attention. Nevertheless, compared with chlorides or bromides, iodides have both a softer Li sublattice and lower reduction limit, which enable iodides to possess potentially high ionic conductivity and intrinsic anti-reduction stability, respectively. Herein, we report a new series of iodide SEs: Lix YI3+x (x=2, 3, 4, or 9). Through synchrotron X-ray/neutron diffraction characterizations and theoretical calculations, we revealed that the Lix YI3+x SEs belong to the high-symmetry cubic structure, and can accommodate abundant vacancies. By manipulating the defects in the iodide structure, balanced Li-ion concentration and generated vacancies enables an optimized ionic conductivity of 1.04 × 10-3  S cm-1 at 25 °C for Li4 YI7 . Additionally, the promising Li-metal compatibility of Li4 YI7 is demonstrated via electrochemical characterizations (particularly all-solid-state Li-S batteries) combined with interface molecular dynamics simulations. Our study on iodide SEs provides deep insights into the relation between high-symmetry halide structures and ionic conduction, which can inspire future efforts to revitalize halide SEs.

Demonstration of the Formation of a Selenocysteine Selenenic Acid through Hydrolysis of a Selenocysteine Selenenyl Iodide Utilizing a Protective Molecular Cradle.

Selenocysteine selenenic acids (Sec-SeOHs) and selenocysteine selenenyl iodides (Sec-SeIs) have long been recognized as crucial intermediates in the catalytic cycle of glutathione peroxidase (GPx) and iodothyronine deiodinase (Dio), respectively. However, the observation of these reactive species remained elusive until our recent study, where we successfully stabilized Sec-SeOHs and Sec-SeIs using a protective molecular cradle. Here, we report the first demonstration of the chemical transformation from a Sec-SeI to a Sec-SeOH through alkaline hydrolysis. A stable Sec-SeI derived from a selenocysteine methyl ester was synthesized using the protective cradle, and its structure was determined by crystallographic analysis. The alkaline hydrolysis of the Sec-SeI at -50 °C yielded the corresponding Sec-SeOH in an 89% NMR yield, the formation of which was further confirmed by its reaction with dimedone. The facile and nearly quantitative conversion of the Sec-SeI to the Sec-SeOH not only validates the potential involvement of this process in the catalytic mechanism of Dio, but also highlights its utility as a method for producing a Sec-SeOH.

Target and non-target analyses of neutral per- and polyfluoroalkyl substances from fluorochemical industries using GC-MS/MS and GC-TOF: Insights on their environmental fate.

Novel and emerging per- and polyfluoroalkyl substances (PFAS) are a key issue of concern in global environmental studies. In this study, air, sediment, and wastewater samples were collected from areas in and/or surrounded by fluorochemical-related industrial facilities to characterize the contamination profiles of neutral and novel PFAS (n-PFAS) using a gas chromatograph-based target and non-target analyses. Fluorotelomer alcohols were predominant in the samples, accounting for 80 % of the n-PFAS, followed by fluorotelomer acrylates. Air samples collected proximate to the durable water repellent (DWR) facility had the highest concentration of n-PFAS, which was approximately two orders of magnitude higher than those found in others. Non-target analysis identified fluorotelomer iodides and fluorotelomer methacrylate in multiple matrices near DWR facilities, indicating significant contamination of n-PFAS. Levels of both C6- and C8-based PFAS reflected a shift in usage patterns from C8- to C6-based fluorochemicals. Matrix-dependent profiles of n-PFAS revealed that shorter-chain (e.g., C6) and longer-chain (>C8) PFAS were predominant in air and sediment, respectively, implying that air and sediment are mobile and secondary sources of PFAS. Untreated and treated industrial wastewater also contained n-PFAS and their transformation products. The findings shed light on our understanding of the multi-matrix distribution and transport of PFAS.

Synthesis and Crystal Structure of the Europium(II) Hydride Oxide Iodide Eu5H2O2I4 Showing Blue-Green Luminescence.

As the first europium(II) hydride oxide iodide, dark red single crystals of Eu5H2O2I4 could be synthesized from oxygen-contaminated mixtures of EuH2 and EuI2. Its orthorhombic crystal structure (a = 1636.97(9) pm, b = 1369.54(8) pm, c = 604.36(4) pm, Z = 4) was determined via single-crystal X-ray diffraction in the space group Cmcm. Anion-centred tetrahedra [HEu4]7+ and [OEu4]6+ serve as central building blocks interconnected via common edges to infinite ribbons parallel to the c axis. These ribbons consist of four trans-edge connected (Eu2+)4 tetrahedra as repetition unit, two H--centred ones in the inner part, and two O2--centred ones representing the outer sides. They are positively charged, according to ∞1{[Eu5H2O2]4+}, to become interconnected and charge-balanced by iodide anions. Upon excitation with UV light, the compound shows blue-green luminescence with the shortest Eu2+ emission wavelength ever observed for a hydride derivative, peaking at 463 nm. The magnetic susceptibility of Eu5H2O2I4 follows the Curie-Weiss law down to 100 K, and exhibits a ferromagnetic ordering transition at about 10 K.

Iodine-triphenylphosphine triggers an easy one-pot alpha stereoselective dehydrative glycosylation on hemiacetalic benzylated glycosyl donors.

The discovery of new glycosylation reactions is still a major challenge in carbohydrate chemistry. Traditional glycosylation reactions require the preparation of sugar donors with anomeric active or latent leaving groups. Dehydrative glycosylation is a fascinating alternative that enables the direct formation of the glycosidic bond from the hemiacetal, eliminating the need for (sometimes unstable) leaving groups, and allowing to reduce reaction, work-up, and purification times. Although some interesting methods of dehydrative glycosylation have been reported, in order to compete with conventional chemical glycosylation, a greater number of efficient and stereoselective methods need to be developed. Herein, a dehydrative procedure that uses a combination of iodine, triphenylphosphine, and a base (DMAP or imidazole) is described. This methodology allows for the preparation of sugar derivatives from commercially available 1-hydroxy glycosyl donors. The reaction takes place under mild conditions through the in situ-formation of an anomeric iodide intermediate, which, upon reaction with an alcohol, gives the corresponding glycosides up to quantitative yields and with high α-stereoselectivity.

Carbon Dioxide Cycloaddition to Epoxides Promoted by Nicotinamidium Halide Catalysts: A DFT Investigation.

The utilization of CO2 as building block for the production of cyclic carbonate is a promising route to simultaneously mitigate the global warming issue and obtain valuable commercial chemicals. In this work, the activity of nicotinamidium halide catalysts towards the CO2 conversion into cyclic carbonate has been explored by means of density functional theory (DFT) calculations. DFT calculations support the ability, suggested experimentally, of the pyridium α-C-H proton of the catalysts to activate the epoxide ring via a hydrogen bond. Interestingly, DFT calculations underline the involvement of the n-octyl substituent of the pyridyl ring in the epoxide activation, while the hydrogen atom of the amide group N-H is rather involved in the stabilization of the iodide trough electrostatic interactions. Moreover, the replacement of the pyridium α-C-H proton with the bulkier methyl group leads to a different reaction mechanism. The calculated energy barriers well reproduce the experimental trends of the studied catalysts, and the computed activation barrier of 29.0 kcal/mol, relative to the ring opening step of the most active catalyst, is in line with the experimental working temperature of 80 °C. Those results shed light on the CO2 fixation reaction contributing to the development of more efficient catalytic systems.

Structural, Electric and Dynamic Properties of (Pyrrolidinium)3[Bi2I9] and (Pyrrolidinium)3[Sb2I9]: New Lead-Free, Organic-Inorganic Hybrids with Narrow Band Gaps.

Hybrid organic-inorganic iodides based on Bi(III) and Sb(III) provide integrated functionalities through the combination of high dielectric constants, semiconducting properties and ferroic phases. Here, we report a pyrrolidinium-based bismuth (1) and antimony (2) iodides of (NC4H10)3[M2I9] (M: Bi(III), Sb(III)) formula which are ferroelastic at room temperature. The narrow band gaps (~2.12 eV for 1 and 2.19 eV for 2) and DOS calculations indicate the semiconducting characteristics of both materials. The crystal structure consists of discrete, face-sharing bioctahedra [M2I9]3- and disordered pyrrolidinium amines providing charge balance and acting as spacers between inorganic moieties. At room temperature, 1 and 2 accommodate orthorhombic Cmcm symmetry. 1 displays a complex temperature-induced polymorphism. It is stable up to 525 K and undergoes a sequence of low-temperature phase transitions (PTs) at 221/222 K (I ↔ II) and 189/190 K (II ↔ III) and at 131 K (IV→III), associated with the ordering of pyrrolidinium cations and resulting in Cmcm symmetry breaking. 2 undergoes only one PT at T = 215 K. The dielectric studies disclose a relaxation process in the kilohertz frequency region, assigned to the dynamics of organic cations, described well by the Cole-Cole relation. A combination of single-crystal X-ray diffraction, synchrotron powder diffraction, spin-lattice relaxation time of 1H NMR, dielectric and calorimetric studies is used to determine the structural phase diagram, cation dynamics and electric properties of (NC4H10)3[M2I9].

Closing the Cycle as It Begins: Synthesis of ortho-Iodobiaryls via Catellani Reaction.

Despite the advances in the field of carbon-halogen bond formation, the straightforward catalytic access to selectively functionalized iodoaryls remains a challenge. Here, we report a one-pot synthesis of ortho-iodobiaryls from aryl iodides and bromides by palladium/norbornene catalysis. This new example of Catellani reaction features the initial cleavage of a C(sp2 )-I bond, followed by the key formation of a palladacycle through ortho C-H activation, the oxidative addition of an aryl bromide and the ultimate restoration of the C(sp2 )-I bond. A large variety of valuable o-iodobiaryls has been synthesized in satisfactory to good yields and their derivatization have been described too. Beyond the synthetic utility of this transformation, a DFT study provides insights on the mechanism of the key reductive elimination step, which is driven by an original transmetallation between palladium(II)-halides complexes.

Transition-metal-free Synthesis of tetra-substituted Vinyl Iodides by Cascade Sequential Reaction of α-Keto Acids, 1-Iodoalkynes, and Alkyl Halides.

The cascade sequential reaction of α-keto acids, 1-iodoalkynes, and alkyl halides are reported herein to synthesize tetra-substituted vinyl iodides. It represents an efficient protocol to access a diverse range of tetra-substituted vinyl iodides starting from simple materials in a one-pot fashion, featuring mild reaction conditions, ease of operation, and broad substrate scope.

Rhodium-Catalyzed Anti-Markovnikov Transfer Hydroiodination of Terminal Alkynes.

A rhodium-catalyzed anti-Markovnikov hydroiodination of aromatic and aliphatic terminal alkynes is reported. Depending on the choice of ligand and substrate, either (E)- or (Z)-configured alkenyl iodides are obtained in high to exclusive isomeric purity. The reaction exhibits a broad substrate scope and high functional group tolerance, employing easily accessible or commercially available aliphatic iodides as HI surrogates through a shuttle process. The synthesized vinyl iodides were applied in several C-C and C-heteroatom bond-forming reactions with full retention of the stereoselectivity. The developed method could be used to significantly shorten the total synthesis of a marine cis-fatty acid. Additionally, initial deuterium-labeling experiments and stoichiometric reactions shed some light on the potential reaction mechanism.

Targeted Suppression of Peptide Degradation in Ag-Based Surface-Enhanced Raman Spectra by Depletion of Hot Carriers.

Sample degradation, in particular of biomolecules, frequently occurs in surface-enhanced Raman spectroscopy (SERS) utilizing supported silver SERS substrates. Currently, thermal and/or photocatalytic effects are considered to cause sample degradation. This paper establishes the efficient inhibition of sample degradation using iodide which is demonstrated by a systematic SERS study of a small peptide in aqueous solution. Remarkably, a distinct charge separation-induced surface potential difference is observed for SERS substrates under laser irradiation using Kelvin probe force microscopy. This directly unveils the photocatalytic effect of Ag-SERS substrates. Based on the presented results, it is proposed that plasmonic photocatalysis dominates sample degradation in SERS experiments and the suppression of typical SERS sample degradation by iodide is discussed by means of the energy levels of the substrate under mild irradiation conditions. This approach paves the way toward more reliable and reproducible SERS studies of biomolecules under physiological conditions.

Cesium Lead Iodide Perovskites: Optically Active Crystal Phase Stability to Surface Engineering.

Among perovskites, the research on cesium lead iodides (CsPbI3) has attracted a large research community, owing to their all-inorganic nature and promising solar cell performance. Typically, the CsPbI3 solar cell devices are prepared at various heterojunctions, and working at fluctuating temperatures raises questions on the material stability-related performance of such devices. The fundamental studies reveal that their poor stability is due to a lower side deviation from Goldschmidt's tolerance factor, causing weak chemical interactions within the crystal lattice. In the case of organic-inorganic hybrid perovskites, where their stability is related to the inherent chemical nature of the organic cations, which cannot be manipulated to improve the stability drastically whereas the stability of CsPbI3 is related to surface and lattice engineering. Thus, the challenges posed by CsPbI3 could be overcome by engineering the surface and inside the CsPbI3 crystal lattice. A few solutions have been proposed, including controlled crystal sizes, surface modifications, and lattice engineering. Various research groups have been working on these aspects and had accumulated a rich understanding of these materials. In this review, at first, we survey the fundamental aspects of CsPbI3 polymorphs structure, highlighting the superiority of CsPbI3 over other halide systems, stability, the factors (temperature, polarity, and size influence) leading to their phase transformations, and electronic band structure along with the important property of the defect tolerance nature. Fortunately, the factors stabilizing the most effective phases are achieved through a size reduction and the efficient surface passivation on the delicate CsPbI3 nanocrystal surfaces. In the following section, we have provided the up-to-date surface passivating methods to suppress the non-radiative process for near-unity photoluminescence quantum yield, while maintaining their optically active phases, especially through molecular links (ligands, polymers, zwitterions, polymers) and inorganic halides. We have also provided recent advances to the efficient synthetic protocols for optically active CsPbI3 NC phases to use readily for solar cell applications. The nanocrystal purification techniques are challenging and had a significant effect on the device performances. In part, we summarized the CsPbI3-related solar cell device performances with respect to the device fabrication methods. At the end, we provide a brief outlook on the view of surface and lattice engineering in CsPbI3 NCs for advancing the enhanced stability which is crucial for superior optical and light applications.

Important effects of relative humidity on the formation processes of iodine oxide particles from CH3I photo-oxidation.

In this work, laboratory chamber experiments of gas-phase methyl iodide photolysis in the presence of ozone at three relative humidity conditions were performed to study the formation and physico-chemical properties of iodine oxide particles. The obtained results revealed significant morphological changes of iodine oxide particles that were observed to depend on relative humidity. The formed iodine oxide particles under dry conditions were supposed to be agglomerates of fine hygroscopic crystals. On the other hand, a humid atmosphere was observed to favor the formation of isomeric, tetragonal and orthorhombic hygroscopic crystals potentially composed of HIO3 likely formed from progressive hydration of iodine oxide clusters. This process leads to a release of molecular iodine, I2, which may indicate a potential role of I2O4 in the particles' evolution processes. The obtained results on the iodine oxides' behavior are important to the nuclear power plant safety industry since many of the organic iodides that may be released during a major nuclear power-plant accident contain radioactive isotopes of iodine that are known to have lethal or toxic impacts on human health.

Highly Chemoselective Transamidation of Unactivated Tertiary Amides by Electrophilic N-C(O) Activation by Amide-to-Acyl Iodide Re-routing.

The challenging transamidation of unactivated tertiary amides has been accomplished via cooperative acid/iodide catalysis. Most crucially, the method provides a novel manifold to re-route the reactivity of unactivated N,N-dialkyl amides through reactive acyl iodide intermediates, thus reverting the classical order of reactivity of carboxylic acid derivatives. This method provides a direct route to amide-to-amide bond interconversion with excellent chemoselectivity using equivalent amounts of amines. The combination of acid and iodide has been identified as the essential factor to activate the amide C-N bond through electrophilic catalytic activation, enabling the production of new desired transamidated products with wide substrate scope of both unactivated amides and amines, including late-stage functionalization of complex APIs (>80 examples). We anticipate that this powerful activation mode of unactivated amide bonds will find broad-ranging applications in chemical synthesis.

Modeling of selenocysteine-derived reactive intermediates utilizing a nano-sized molecular cavity as a protective cradle.

In the biological functions of selenoproteins, various highly reactive species formed by oxidative modification of selenocysteine residues have been postulated to play crucial roles. Representative examples of such species are selenocysteine selenenic acids (Sec-SeOHs) and selenocysteine selenenyl iodides (Sec-SeIs), which have been widely recognized as important intermediates in the catalytic cycle of glutathione peroxidase (GPx) and iodothyronine deiodinase, respectively. However, examples of even spectroscopic observation of Sec-SeOHs and Sec-SeIs in either protein or small-molecule model systems remain elusive so far, most likely due to their notorious instability. For the synthesis of small-molecule model compounds of these reactive species, it is essential to suppress their very facile bimolecular decomposition such as self-condensation and disproportionation. Here we outline a novel method for the synthesis of stable small-molecule model compounds of the selenocysteine-derived reactive species, in which a nano-sized molecular cavity is used as a protective cradle to accommodate the reactive selenocysteine unit. Stabilization by the molecular cradle led to the successful synthesis of Sec-SeOHs, which are stable in solution at low temperatures, and a Sec-SeI, which can be isolated as crystals. The catalytic cycle of GPx was investigated using the NMR-observable Sec-SeOH models, and all the chemical processes proposed for the catalytic cycle of GPx, including the bypass process from Sec-SeOH to the corresponding cyclic selenenyl amide, were experimentally confirmed. Detailed protocols for the syntheses of selenopeptide derivatives bearing the molecular cradle and for the spectroscopic monitoring of their reactions are provided.

Nickel-Catalyzed Reductive Allyl-Aryl Cross-Electrophile Coupling via Allylic C-F Bond Activation.

Nickel-catalyzed reductive cross-coupling of allylic difluorides with aryl iodides was achieved via allylic C-F bond activation. Based on this protocol, a series of γ-arylated monofluoroalkenes were synthesized in moderate to high yields with high Z-selectivities. Mechanistic studies suggest that the C-I bonds of the aryl iodides and the C-F bonds of the allylic difluorides were cleaved via oxidative addition and ß-fluorine elimination, respectively, where the oxidative addition of less reactive C-F bonds was avoided to permit their transformation.