Iodine Atoms Research Articles

Two-photon absorption laser induced fluorescence (TALIF) detection of atomic iodine in low-temperature plasmas and a revision of the energy levels of I I

In order to perfect the use of iodine, instead of xenon, in plasma thrusters, an experiment has been set up to investigate the feasibility of two-photon absorption laser induced fluorescence (TALIF) diagnostics in iodine plasmas. Levels and of atomic iodine were found qualified for that purpose, with a radiative lifetime of the former found equal to , which appears consistent with the predicted by the most recent calculations. Doppler-free two-photon spectroscopy has confirmed that the relative intensities of the hyperfine components follow well-known general formulas, which makes it possible to disentangle the hyperfine structure of from Doppler broadening. Accurate temperature measurements are shown to be possible, even though the relatively heavy mass of the iodine atom does not make it the most favorable gauge for measurements based on Doppler effect. Using an injection seeded pulsed laser as the primary laser source, the frequency-tripling of which has provided the ca 300 nm radiation used for excitation, absolute energy measurements of the two-photon excited levels revealed that all upper energy levels of I I have to be revised down, by , which pulls every energy level off its presently tabulated value by more than thirty times the currently admitted uncertainty bar.

Direct identification of amino acid-derived hormones with single-atom resolution using an engineered aerolysin nanopore.

The amino acid-derived hormones (AAHs), which are relatively small hydrophobic molecules derived from the amino acid tyrosine and tryptophan, play critical roles in the regulation of organism development and metabolism process. Direct identification of AAHs and their metabolites is highly desirable but very challenging because they simultaneously possess the features of small volume, hydrophobicity and highly structural similarity. Nanopore, capable of sensing the analytes in a single-molecule manner, may be engineered to identity AAHs. The key aporia is the ion current instability caused by the introduction of hydrophobic amino acids inside the nanopore confinement that is essential to improve the spatial and temporal resolution for small hydrophobic molecules sensing. Herein, we design a mutant aerolysin that precisely introduces a hydrophobic chemical environment in the critical sensing region with a highly controlled hydrogen bonds network to balance the ion follow stability and hydrophobic interactions. With this hydrophobic enhanced aerolysin nanopore, direct identification of AAHs was achieved, including thyroid hormone, pineal hormone and adrenal medullary hormone. Furthermore, three thyroid hormones with single iodine atom difference (T4, T3, and T2), were observed to be clearly discriminated in their mixture. Our engineered nanopore can even distinguish isomers of T3 and rT3 that vary only slightly in structure. Assisted with a custom clustering machine learning algorithm, the thyroid hormones T4, T3, and T2 in their mixture could be quantified, which suggests a simple and rare approach to measure the AAHs in clinical samples.

Electrochemical degradation of contrast media

This work provides a critical review about the most recent works in electrochemical remediation of wastewater containing contrast media, very concerning pollutants resistant to conventional treatments in wastewater treatment plants. The focus is on iodinated contrast media and gadolinium-based contrast agents (GBCAs). After a short introduction in which non-electrochemical methods are presented, electro-oxidative and electro-reductive methods are discussed in the former case. A short section is also dedicated to methods based on a combination of the two. In the case of GBCAs, a brief presentation of non-electrochemical techniques is also reported, followed by some electrochemical treatments for Gd 3+ . Considering the lack of literature on the use of electrochemical methods for the removal of this type of magnetic resonance imaging contrast agents, the potential of electrochemistry for the degradation in this field is then explored. • Contrast media in water can be successfully removed using various electrochemical oxidation, even in complex matrices. • Electrochemical reduction can help in removing iodine atoms from Iodinated contrast media, making them more biodegradable. • The combination of electrochemical oxidation and reduction showed a good mineralisation of the compounds.

Charge Transfer Reactions from I- to Polar Protic Solvents Studied Using Ultrafast Extreme Ultraviolet Photoelectron Spectroscopy.

Charge transfer reactions from I- to solvent water, methanol, and ethanol were studied using extreme ultraviolet time-resolved photoelectron spectroscopy (EUV-TRPES). This technique eliminates spectral broadening, previously seen in UV-TRPES, caused by electron inelastic scattering in liquids, and enables clear observation of the temporal evolution of the spectral shape. The peak position, width, and intensity of the electron binding energy distribution indicate electron detachment and subsequent solvation and thermalization processes. Geminate recombination between detached electrons and iodine atoms is discussed using a diffusion equation and a global fitting analysis based on a kinetics model.

EU proposal would restrict PFAS

The European Union is considering a proposal that would restrict the manufacture, sale, and use of per- and polyfluoroalkyl substances (PFAS) . This plan would regulate PFAS as a group rather than individual compounds, as is now the case. These chemicals are valued for traits including water and grease resistance and ability to withstand harsh conditions. They are highly persistent in the environment, and some are toxic at very low levels. The European Chemicals Agency (ECHA) announced Jan. 18 that it had received the PFAS proposal from Germany, Denmark, the Netherlands, Norway, and Sweden. The proposal would define PFAS as “substances that contain at least one fully fluorinated methyl (–CF 3 ) or methylene (–CF 2 –) carbon atom” that is not also attached to a hydrogen, chlorine, bromine, or iodine atom. This is similar to a 2021 definition of PFAS from the Organisation for Economic Co-operation and Development. ECHA

Probing the Potential Energy Profile of the I + (H2O)3 → HI + (H2O)2OH Forward and Reverse Reactions: High Level CCSD(T) Studies with Spin-Orbit Coupling Included.

Three different pathways for the atomic iodine plus water trimer reaction I + (H2O)3 → HI + (H2O)2OH were preliminarily examined by the DFT-MPW1K method. Related to previous predictions for the F/Cl/Br + (H2O)3 reactions, three pathways for the I + (H2O)3 reaction are linked in terms of geometry and energetics. To legitimize the results, the "gold standard" CCSD(T) method was employed to investigate the lowest-lying pathway with the correlation-consistent polarized valence basis set up to cc-pVQZ(-PP). According to the CCSD(T)/cc-pVQZ(-PP)//CCSD(T)/cc-pVTZ(-PP) results, the I + (H2O)3 → HI + (H2O)2OH reaction is predicted to be endothermic by 47.0 kcal mol-1. The submerged transition state is predicted to lie 43.7 kcal mol-1 above the separated reactants. The I···(H2O)3 entrance complex lies below the separated reactants by 4.1 kcal mol-1, and spin-orbit coupling has a significant impact on this dissociation energy. The HI···(H2O)2OH exit complex is bound by 4.3 kcal mol-1 in relation to the separated products. Compared with simpler I + (H2O)2 and I + H2O reactions, the I + (H2O)3 reaction is energetically between them in general. It is speculated that the reaction between the iodine atom and the larger water clusters may be energetically analogous to the I + (H2O)3 reaction. The iodine reaction I + (H2O)3 is connected with the analogous valence isoelectronic bromine/chlorine reactions Br/Cl + (H2O)3 but much different from the F + (H2O)3 reaction. Significant difference with other halogen systems, especially for barrier heights, are seen for the iodine systems.

Chitosan Composites Containing Boron-Dipyrromethene Derivatives for Biomedical Applications.

The work is devoted to preparing and characterizing the properties of photosensitive composites, based on chitosan proposed for photodynamic therapy. Chitosan films with a 5% addition of two BODIPY dyes were prepared by solution casting. These dyes are dipyrromethene boron derivatives with N-alkyl phthalimide substituent, differing in the presence of iodine atoms in positions 2 and 6 of the BODIPY core. The spectral properties of the obtained materials have been studied by infrared and UV-vis absorption spectroscopy and fluorescence, both in solutions and in a solid state. Surface properties were investigated using the contact angle measurement. The morphology of the sample has been characterized by Scanning Electron and Atomic Force Microscopy. Particular attention was paid to studying the protein absorption and kinetics of the dye release from the chitosan. Adding BODIPY to the chitosan matrix leads to a slight increase in hydrophilicity, higher structure heterogeneity, and roughness, than pure chitosan. The presence of iodine atoms in the BODIPY structure caused the bathochromic effect, but the emission quantum yield decreased in the composites. It has been found that BODIPY-doped chitosan interacts better with human serum albumin and acidic α-glycoprotein than unmodified chitosan. The release rate of dyes from films immersed in methanol depends on the iodine present in the structure.

How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes.

The crystal structures of two isomeric triiodo derivatives of ortho-carborane containing substituents in the three most electron-withdrawing positions of the carborane cage, 1,2,3-I3-1,2-C2B10H9, and the three most electron-donating positions, 8,9,12-I3-1,2-C2B10H9, as well as the crystal structure of 8,9,12-Br3-1,2-C2B10H9, were determined by single-crystal X-ray diffraction. In the structure of 1,2,3-I3-1,2-C2B10H9, an iodine atom attached to the boron atom (position 3) donates its lone pairs simultaneously to the σ-holes of both iodine atoms attached to the carbon atoms (positions 1 and 2) with the I⋯I distance of 3.554(2) Å and the C-I⋯I and B-I⋯I angles of 169.2(2)° and 92.2(2)°, respectively. The structure is additionally stabilized by a few B-H⋯I-shortened contacts. In the structure of 8,9,12-I3-1,2-C2B10H9, the I⋯I contacts of type II are very weak (the I⋯I distance is 4.268(4) Å, the B8-I8⋯I12 and B12-I12⋯I8 angles are 130.2(3)° and 92.2(3)°) and can only be regarded as dihalogen bonds formally. In comparison with the latter, the structure of 8,9,12-Br3-1,2-C2B10H9 demonstrates both similarities and differences. No Br⋯Br contacts of type II are observed, while there are two Br⋯Br halogen bonds of type I.

Electronic Modulation of Semimetallic Electrode for 2D van der Waals Devices

The 2D semimetallic electrodes have been employed to show outstanding contact properties with 2D semiconducting transition‐metal dichalcogenides (TMDCs) channel, leading to large enhancement of 2D transistor and phototransistor performance. Herein, an innovative concept is established for a unique 2D semimetallic electrode‐2D TMDC channel (2D–2D) device configuration where the electronic structures of 2D semimetallic electrodes are systematically modulated to improve the contact properties with 2D monolayer molybdenum disulfide (MoS2) channel. The 2D semimetallic copper sulfide (CuS) electrodes are doped with iodine atoms by a direct exposure of iodine gas. The contact properties and charge‐transport behavior in the 2D–2D field‐effect transistors (FETs) are highly improved, which is attributed to the favorable energy band alignment and associated material properties between the iodine‐doped CuS (CuS–I) electrodes and 2D channel. The 2D–2D FETs show a high on current, high on/off ratio, and twofold improvement in mobility. Furthermore, 2D–2D phototransistors and flexible/transparent photodetectors are fabricated using the CuS–I/MoS2, which also performed outstanding photoresponsivity characteristics and mechanical durability under external bending strain conditions. These findings demonstrate a promising pathway that under the 2D–2D configuration, the electronic modulation by the iodine atoms may enable the development of future 2D electronic applications.

Effect of Solubilizing Group on the Antibacterial Activity of Heptamethine Cyanine Photosensitizers.

Antibiotic resistance of pathogenic bacteria dictates the development of novel treatment modalities such as antimicrobial photodynamic therapy (APDT) utilizing organic dyes termed photosensitizers that exhibit a high cytotoxicity upon light irradiation. Most of the clinically approved photosensitizers are porphyrins that are poorly excitable in the therapeutic near-IR spectral range. In contrast, cyanine dyes function well in the near-IR region, but their phototoxicity, in general, is very low. The introduction of iodine atoms in the cyanine molecules was recently demonstrated to greatly increase their phototoxicity. Herein, we synthesized a series of the new iodinated heptamethine cyanine dyes (ICy7) containing various solubilizing moieties, i.e., negatively charged carboxylic (ICy7COOH) and sulfonic (ICy7SO3H) groups, positively charged triphenylphosphonium (ICy7PPh3), triethylammonium (ICy7NEt3) and amino (ICy7NH2) groups, and neutral amide (ICy7CONHPr) group. The effect of these substituents on the photodynamic eradication of Gram-positive (S. aureus) and Gram-negative (E. coli and P. aeruginosa) pathogens was studied. Cyanine dyes containing the amide and triphenylphosphonium groups were found to be the most efficient for eradication of the investigated bacteria. These dyes are effective at low concentrations of 0.05 µM (33 J/cm2) for S. aureus, 50 µM (200 J/cm2) for E. coli, and 5 µM (100 J/cm2) for P. aeruginosa and considered, therefore, promising photosensitizers for APDT applications. The innovation of the new photosensitizers consisted of a combination of the heavy-atom effect that increases singlet oxygen generation with the solubilizing group's effect improving cell uptake, and with effective near-IR excitation. Such a combination helped to noticeably increase the APDT efficacy and should pave the way for the development of more advanced photosensitizers for clinical use.

Scrutinizing Synergy and Active Site of Nitrogen and Selenium Dual-Doped Porous Carbon for Efficient Triiodide Reduction

Electrocatalytic interconversion of iodide/triiodide is the key for state-of-the-art iodine-involved energy technologies, which is challenged by understanding the structure–activity relationship of the smart electrocatalysts with tuned active sites. Herein, active-site-enriched N,Se-co-doped porous carbon, denoted as NSeC, is crafted by a two-step approach of the template method and chemical doping. X-ray photoelectron spectroscopy and synchrotron X-ray absorption spectroscopy measurements substantiate the incorporation of extrinsic N and Se species into the carbon matrix. Raman spectroscopy reveals that the defect of densities within NSeC can be finely tuned by adjusting the doping temperature. The NSeC sample made at 900 °C shows a robust durability and a high electrocatalytic activity toward the triiodide reduction reaction with a relatively small charge-transfer resistance (0.75 Ω cm2) in parallel with a short electron lifetime (252.2 μs) participating in the triiodide reduction. Density functional theory calculations reveal that the high catalytic activity of the NSeC is due to the combined impacts, i.e., the synergy between N and Se species that helps to manipulate the adsorption process of iodine atoms and the active sites formed by the carbon atoms adjacent to quaternary N and Se atoms at the armchair edges. This work offers insights into both the design of efficient metal-free catalysts and the synergy of dual doping for efficient iodine-involved electrocatalysis for energy devices.

Synthesis, structures and reactions of acylsulfenyl iodides with theoretical investigations.

A series of acylsulfenyl iodides (RCOSI) were synthesized by the reactions of carbothioic acid group 11-16 element derivatives with iodine or N-iodosuccinimides in moderate to good yields. The structure of the PhCOSI was nearly square planar based on the X-ray analysis, where the C[double bond, length as m-dash]O⋯I distance (3.153(5) Å) was significantly shorter than the sum of the van der Waals radii of the atoms (Σr vdW), indicating close contact within the molecule. The distances between an iodine atom and the neighbouring two iodine atoms were also less than Σr vdW, perhaps due to the energy lowering effect of the interactions. The acylsulfenyl iodides readily reacted with alkenes and alkynes to give the expected addition products in moderate to good yields at approximately 0 °C. A new synthesis of acylated sulfines, sulfenamides and sulfenochalcogenides using acylsulfenyl iodides is also described. Theoretical calculations were performed on PhCOSI with the Sapporo-TZP(+1s1p) basis sets at the MP2 level, which perfectly reproduced the observed structures. Similar calculations were performed on the reactions, exemplified by those of MeCOSI and CH2[double bond, length as m-dash]CH2, together with those of MeSI and CH2[double bond, length as m-dash]CH2. Mechanisms for both reactions were proposed, which were very similar. The proposed mechanism for the former was understood based on that of the latter. For both mechanisms, the episulfuranes and episulfonium ions played an important role. The dynamic and static nature of the bonds in the COSI group of PhCOSI and MeCOSI were elucidated based on QTAIM dual functional analysis.

Spin-orbit coupling in molecular complexes beyond van der Waals regime: Key factors for further splitting of 2P3/2 ground state

We report a joint spectroscopic and theoretical study probing spin-orbit coupling (SOC) in a variety of molecular complexes between an iodine atom and a ligand (L) with L ranging from Ar, HF to formic/acetic acids, and glycine/N-methylated glycine derivatives. Cryogenic photoelectron spectroscopy of L·I- (L=HCOOH, CH3COOH) reveals three distinct peaks, identified as three SOC states, denoted as X(1/2), A(3/2), and B(l/2) for the corresponding neutrals. The X and A separation ΔEXA is measured to be 0.10 eV for both, whereas the X and B gap ΔEXB is 0.98 and 0.97 eV for formic and acetic acid, respectively. These new ΔEXA values are compared with the previously reported values for the molecular complexes L·I· with L=Ar, HF, glycine, and A-methylated glycines. All together these complexes encompass a diversity of intermolecular interactions, from van der Waals to weak and strong hydrogen bonding. While the ΔEXB remains similar, the ΔEXA is shown to be extremely sensitive to the type of ligands and interactions, spanning from 5 meV to 150 meV. High-level relativistic quantum calculations including explicit SOC formulism nicely reproduce all experimental SOC splitting. A direct correlation between the magnitude of ΔEXA with the intermolecular interaction strength or bond distance of the neutral complexes—the stronger interaction (shorter bond length), the greater splitting, is established.

The Malaprade reaction mechanism for ethylene glycol oxidation by periodic acid based on density functional theory (DFT).

A general mechanism of the Malaprade oxidative carbon-carbon bond cleavage reaction of α-glycol in the presence of periodic acid has been proposed on the basis of density functional theory (DFT) computations. Ethylene glycol and periodic acid, both in their neutral forms, have been studied as noble substrate representatives in model reactions. The proposed reaction mechanism has been constructed based on and compared with previously published experimental kinetic, spectroscopic and temperature and pH-dependent studies. In the presented theoretical mechanistic considerations, four alternative molecular transformations have been analyzed from thermodynamic and kinetic points of view. Theoretically, the predicted activation energy barriers have been compared with experimental ones published elsewhere. The presented minimum energy pathway (MEP) unveiled the shape and conformation of the intermediate and transition state structures. The three-step reaction process involves the formation of a seven-membered quasi-ring assisted by an intramolecular hydrogen-bond intermediate structure forming one I-O bond (IC1_B), a cyclic ester intermediate forming two I-O bonds (IC2_C) and the final products formed at the two very last stages (HIO3, water and two formaldehyde molecules). The computed and energetically the most favourable reaction landscape proposed in this work uniforms and refines the mechanistic proposition given by Criegee for Malaprade type of reactions and further gives a detailed molecular understanding of the reaction rate and atomic connections en route the transformation. The molecular geometries of all stationary points (intermediate and transition state structures) lying on the potential energy hypersurface have been optimized at the four alternative DFT levels under the solvation model based on the density approximation: B3PW91, CAM-B3LYP, BMK, ωB97XD. The 6-311+G(2d,p) basis set for C, O, and H atoms and both the full (DGDZVP) and Ahlrichs-Weigend1 (def2-TZVP) basis sets for iodine atoms were used during the computations.

A Simple Substitution on Thyroid Hormones Remarkably Alters the Regioselectivity of Deiodination by a Deiodinase Mimic.

The regioselective deiodinations of L-thyroxine (T4) play key roles in the thyroid hormone homeostasis. These reactions are catalyzed by three isoforms of the selenoenzymes, iodothyronine deiodinases (Dio1, Dio2 and Dio3), which are highly homologous in nature. Dio1 mediates 5'- or 5-deiodinations of T4 to produce T3 and rT3, respectively. In contrast, Dio2 and Dio3 are selective to 5'- or 5-deiodination to produce T3 and rT3, respectively. Understanding of the regioselectivity of deiodination at the molecular level is important as abnormal levels of thyroid hormone have been implicated in various clinical conditions, such as hypoxia, myocardial infarction, neuronal ischemia and cancer. In this paper, we report that the electronic properties of the iodine atoms in thyroxine (T4) can be modulated through a simple substitution in the 4'-phenolic moiety. This leads to the change in the regioselectivity of deiodination by different small molecule mimics of Dio enzymes. By using this chemical approach, we also show that the substitution of a strong electron withdrawing group facilitates the removal of all four iodine atoms in the T4 derivative. Theoretical investigations on the hydrogen bonded adducts of T4 with imidazole indicate that the charge on the iodine atoms depend on the nature of hydrogen bond between the -OH group of T4 and the imidazole moiety. While the imidazole can act as either hydrogen bond acceptor (HBA) or hydrogen bond donor (HBD), the protonated imidazole acts exclusively as HBD in T4-imidazole complex. These studies support the earlier observations that the histidine residue at the active sites of the deiodinases play an important role not only in the substrate binding, but also in altering the regioselectivity of the deiodination reactions.

Molecular Modification of Lignin-Based Carbon Materials: Influence of Supramolecular Bonds on the Properties

For the application of lignin-based materials, it is necessary to develop simple and efficient chemical modification strategies for lignin. In this work, the iodization modification strategy is selected to improve the specific surface area and graphitization degree of lignin-based carbon fibers. The introduction of an iodine atom can effectively increase the π electron cloud density of the lignin aromatic hydrocarbon structure. High π electron cloud density can effectively enhance the π-π interaction force between lignin molecules (the supramolecular bonds). The biomass precursors with this intermolecular microstructure exhibit good thermal stability and can maintain the original fibrous morphology during high-temperature treatment, which is beneficial for increasing the specific surface area of biomass-based carbon materials. Furthermore, this intermolecular microstructure also contributes to the graphitization of biomass precursor materials and reduces the spacing of graphite micro-lamellae. The obtained lignin-based carbon fibers with iodization modification exhibit a specific capacitance of 333 F/g at a current density of 1 A/g in the three-electrode tests in 6 M KOH solution. As the assembled supercapacitor, the specific capacitance of lignin-based carbon fibers reaches 87 F/g in 1 M Na2SO4 solution. Compared to other modification processes for raw materials, this strategy is simple and efficient and has reference value for the synthesis of other high-performance biomass-based materials.

The effect of various partial atomic charges on the bulk and liquid/vacuum interface properties of iodobenzene derivatives at their melting points

In this work, various atomic charge schemes including natural bond orbital (NBO), electrostatic potential based (CHELPG), and σ-hole model charges were applied in the OPLS-AA force field to investigate their effects on the thermophysical and structural properties of iodobenzene and its derivatives. Molecular dynamics simulations presented in this work show that the studied structural and thermophysical properties are in good agreement with experiments when the CHELPG charge was coupled with the OPLS-AA force field. Also, the arrangement of iodobenzene derivatives in the liquid phase was investigated via combined radial/angular distribution functions (CDFs) analyses and halogen-bonding theory. The most probable orientation of iodobenzene derivatives at the liquid/vacuum interface was assigned by atom density profile and bivariate orientational distribution maps. For all studied iodobenzene derivatives, benzene rings are oriented such that the iodine atoms tend toward the vacuum phase.

Redox impulse, computational calculation of molecular energy potentials and ultra-trace determination of the food colorant erythrosine b in fruit jams, soft drinks and water

The computational calculation of molecular energy potentials and redox behavior are of great importance in view point of prediction of food colorant characteristics such as energy levels, bandgaps of absorption and redox potentials values. Thus, the current study recognizes the electrochemical redox imprints of the underexplored food colorant erythrosine b (E127) in potential sources. The redox impulse and surface coverage (Γ) of the electro active E127 specie implied an explicit adsorptive differential pulse-cathodic stripping voltammetric (Ads-DP-CSV) tool for its trace analysis. Bridging the theoretical and experimental records, a standard sensing route was established to interpret the redox mechanism of E127 at the optimized pH (7.5) upon controlled electrochemical deposition followed by direct Ads-DP-CSV monitoring at −0.73 V on HMDE vs. Ag/AgCl electrode. The highest occupied molecular orbital energy (HOMO) (−4.90 to −4.92 eV) and the lowest unoccupied molecular orbital energy (LUMO) (−2.11 to −2.0 EV) distribution patterns in water and acetonitrile as computed using DFT/B3LYP/3–2G level and the corresponding band gap energy in water (2.8 eV) and acetonitrile (2.92 eV) gave evidence for the cut-off conjugation interaction between the benzoic part and other rings in the E127 molecule to assign the most probable electrochemical reduction mechanism. The negative charge is centered on the highest electronegative atom, oxygen (−0.17 to −0.30), and the positive charge on the iodine atoms (0.14–0.19). This practice was based upon controlled adsorptive deposition of E127 at pH 7.5 followed by direct Ads DP-CSV measurement of the reduced species at HMDE −0.79 V vs. Ag/AgCl electrode. The linear plot of the cathodic peak current (ip,c) at −0.73 V versus concentrations of E127 provided low limits of detection (LOD) and quantification (LOQ) of 0.18 and 0.594 µgL−1, respectively. The probe was robustly subjected to E127 analysis in jams, soft drinks, and water samples.

Characterization of the O-centered vanadium selenoiodides V4OSe8I6·X (X = I2, 3,5-dimethylpyrazole)

O-centered vanadium(IV) selenoiodide V4OSe8I6·3,5-dimethylpyrazole was synthesized in a sealed glass ampoule at moderate temperature 220 °C from the mixture of V, Se, I2, small quantity of water and 3,5-dimethylpyrazole. The X-ray single crystal structure of the compound was solved. The crystal structure includes O-centered tetranuclear complex [V4(μ4-O)(μ-Se2)4(μ-I)2I4] in which vanadium atoms are bridged by diselenide (Se2)2– and iodide I– groups; four terminal iodides coordinate vanadium atoms additionally. Molecules of 3,5-dimethylpyrazole form non-covalent contacts with iodine and selenium atoms of the V4OSe8I6 complexes. Once compounds V4OSe8I6·3,5-dimethylpyrazole and V4OSe8I6·I2 contain similar electroneutral coordination molecular fragment V4OSe8I6, we present here a discussion of spectroscopic properties as well as thermal behavior. Comparing XPS data, both compounds contain vanadium complexes with major V 2p binding energies very similar to each other, and almost equal binding energies in XPS Se 3d and I 3d showing their forms of (Se2–)2 and I–, respectively. Thermolysis character of these compounds revealed higher stability of V4OSe8I6·I2 than V4OSe8I6·3,5-dimethylpyrazole, that indicates a greater stability of the system of non-covalent contacts involving iodine molecules than 3,5-dimethylpyrazole.

Interchangeability and Disorder in the Solid-State Structures of "Two Wall" Calix[4]pyrroles Equipped with Iodine and Ethynyl para-Substituents.

Herein, the synthesis and X-ray structures of three α,β "two wall" aryl-extended calix[4]pyrroles having either identical (symmetrically substituted) or different (non-symmetrically substituted) meso-aryl substituents (aryl=4-ethynylphenyl and 4-iodophenyl) are reported. The X-ray structure of the co-crystal formed by the two symmetrically substituted calix[4]pyrroles is also described. In the solid state, all studied α,β-calix[4]pyrroles exhibit a 1,3-alternate conformation with two co-crystallized acetonitrile solvent molecules H-bonded to adjacent cis-pyrrole rings. Remarkably, the 1,3-conformer of the non-symmetrically substituted iodophenyl/ethynylphenyl compound is intrinsically chiral. The two enantiomers are present in the average asymmetric unit in a 65 : 35 occupancy ratio displaying a head-to-tail directional disorder. This is due to the functional complementarity and the isosteric and isoelectronic properties of the para-substituents: iodo and ethynyl. That is, the negative belt of iodine is similar to the negative π-system of the C≡C triple bond and the σ-hole in the iodine atom is similar to the positive proton at the C≡C-H group.