CH CN Research Articles

Boosting CO2 Photoreduction to Formate or CO with High Selectivity over a Covalent Organic Framework Covalently Anchored on Graphene Oxide.

Covalent organic frameworks (COFs) have been widely studied in photocatalytic CO2 reduction reaction (CO2 RR). However, pristine COFs usually exhibit low catalytic efficiency owing to the fast recombination of photogenerated electrons and holes. In this study, we fabricated a stable COF-based composite (GO-COF-366-Co) by covalently anchoring COF-366-Co on the surface of graphene oxide (GO) for the photocatalytic CO2 reduction. Interestingly, in absolute acetonitrile (CH3 CN), GO-COF-366-Co shows a high selectivity of 94.4 % for the photoreduction of CO2 to formate, with a formate yield of 15.8 mmol/g, which is approximately four times higher than that using the pristine COF-366-Co. By contrast, in CH3 CN/H2 O (v : v=4 : 1), the main product for the photocatalytic CO2 reduction over GO-COF-366-Co is CO (96.1 %), with a CO yield as high as 52.2 mmol/g, which is also approximately four times higher than that using the pristine COF-366-Co. Photoelectrochemical experiments demonstrate the covalent bonding of COF-366-Co and GO to form the GO-COF-366-Co composite facilitates charge separation and transfer significantly, thereby accounting for the enhanced catalytic activity. In addition, theoretical calculations and in situ Fourier transform infrared spectroscopy reveal H2 O can stabilize the *COOH intermediate to further form a *CO intermediate via O-H(aq)⋅⋅⋅O(*COOH) hydrogen bonding, thus explaining the regulated photocatalytic performance.

Bis(N-Heterocyclic Carbene) Manganese(I) Complexes in Catalytic N-Formylation/N-Methylation of Amines Using Carbon Dioxide and Phenylsilane.

A series of six Mn(I) complexes with general formula [MnBr(bisNHC)(CO)3 ], having a bidentate bis(N-heterocyclic carbene) ligand (bisNHC), has been developed by varying the bridging group between the NHC donors, the nitrogen wingtip substituents and the heterocyclic ring. The synthesis of the complexes has been accomplished by in situ transmetalation of the bisNHC from the corresponding silver(I) complexes. Removal of the bromide anion affords the corresponding solvento complexes [Mn(bisNHC)(CO)3 (CH3 CN)](BF4 ). The influence of the bisNHC structure on its electron donor ability has been evaluated by FTIR and 13 C NMR spectroscopy, both in the neutral and cationic complexes. Finally, the isolated Mn(I)-bisNHC complexes have been employed as homogeneous catalysts in the reductive N-formylation and N-methylation of amines with CO2 as C1 source and phenylsilane as reducing agent, showing a high selectivity for the N-methylated product. Preliminary mechanistic investigations suggest that, in the adopted reaction conditions, the formylated product can be formed via different reaction pathways, either metal-catalyzed or not, while the methylation reaction requires the use of the Mn(I) catalyst.

Synthesis of Transparent CuI Thin Films by a Facile Low-Cost High Pressure (HP)-PECVD Method at Room Temperature for the Application in Solar Cells.

Copper iodide (CuI) thin films were prepared on a glass substrate by a facile high pressure (HP)-PECVD method at room temperature. For this, CuI powder was dissolved in CH3 CN. The CuI vapor with plasma was investigated by Optical Emission Spectroscopic (OES) data for identifying the species in the plasma. The XRD study reveals the polycrystalline nature of the films. The SEM analyses indicate the homogeneity of the films. The EDS mapping confirms that the thin films mostly consisted of carbon followed by nitrogen, copper and iodine, respectively. The band gaps of CuI thin films were in the range of ~2.71-3.14 eV. The high transmittance and band gap engineering in HP-PECVD-synthesized CuI thin films indicates their potential use as window and hole transport layers in low cost solar cells.

Tunable Synthesis of Monofluoroalkenes and Gem-Difluoroalkenes via Solvent-Controlled Rhodium-Catalyzed Arylation of 1-Bromo-2,2-difluoroethylene.

Divergent synthesis of fluorine-containing scaffolds starting from a suite of raw materials is an intriguing topic. Herein, we report the solvent-controlled rhodium-catalyzed tunable arylation of 1-bromo-2,2-difluoroethylene. The selection of the reaction solvents provides switchable defluorinated or debrominated arylation from readily available feedstock resources (both arylboronic acids/esters and 1-bromo-2,2-difluoroethylene are commercially available). This switch is feasible because of the difference in coordination ability between the solvent (CH2 Cl2 or CH3 CN) and the rhodium center, resulting in different olefin insertion. This protocol allows the convenient synthesis of monofluoroalkenes and gem-difluoroalkenes, both of which are important scaffolds in the fields of medicine and materials. Moreover, this newly developed solvent-regulated reaction system can be applied to the site-selective dechlorinated arylation of trichloroethylene. Overall, this study provides a useful strategy for the divergent synthesis of fluorine-containing scaffolds and provides insight into the importance of solvent selection in catalytic reactions.

Dimetalloylene (M-E-M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E-X Bonds (X = N(SiMe3)2, OtBu) with an Iridium Hydride.

Reactions of the Ir(V) hydride [MeBDIDipp]IrH4 {BDI = (Dipp)NC(Me)CH(Me)CN(Dipp); Dipp = 2,6-iPr2C6H3} with E[N(SiMe3)2]2 (E = Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([MeBDIDipp]IrH)2(μ2-E)2 in good yields. Moreover, ([MeBDIDipp]IrH)2(μ2-Ge)2 was formed in situ from thermal decomposition of [MeBDIDipp]Ir(H)2Ge[N(SiMe3)2]2. These reactions are accompanied by liberation of HN(SiMe3)2 and H2 by the apparent cleavage of an E-N(SiMe3)2 bond by Ir-H. In a reversal of this process, ([MeBDIDipp]IrH)2(μ2-E)2 reacted with excess H2 to regenerate [MeBDIDipp]IrH4. Variations of the concentrations of reactants led to formation of the trimeric ([MeBDIDipp]IrH2)3(μ2-E)3. The further scope of this synthetic route was investigated with group 15 amides, and ([MeBDIDipp]IrH)2(μ2-Bi)2 was prepared via the reaction of [MeBDIDipp]IrH4 with Bi(NMe2)3 or Bi(O t Bu)3, to afford the first example of a 'naked' two-coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for formation of the products is proposed. Computational investigations of the Ir2E2 (E = Ge, Sn, Pb) compounds characterized them as open-shell singlets with confined nonbonding lone-pairs at the E centers. In contrast, Ir2Bi2 is characterized as having a closed-shell singlet ground state.

CH3 CN@open-C60 : An Effective Inner-Space Modification and Isotope Effect Inside a Nano-Sized Flask.

Despite several small molecules being encapsulated inside cage-opened fullerene derivatives, such species have not considerably affected the structures and properties of the outer carbon cages. Herein, we achieved an effective inner-space modification for an open-cage C60 derivative by insertion of a neutral CH3 CN molecule into the cavity. The CH3 CN@open-C60 thus obtained showed an enhanced polarity, thus affording an easy separation from a mixture containing the empty cage by column chromatography on silica gel, without the preparative HPLC that was needed for previous cases. The less negative reduction potentials with respect to those of empty cage reflect the decreased energy level of the LUMO, which is supported by the DFT calculations. NMR spectroscopy, single-crystal X-ray analysis, and theoretical calculations revealed that both the presence of the encapsulated CH3 CN and cage deformation caused by the CH3 CN play an essential role in the change of the electronic properties. Furthermore, the favored binding affinity of deuterated acetonitrile CD3 CN with internal C60 surface is discussed.

Highly Efficient and Selective Visible-light Photocatalytic CO2 Reduction to CO Using a 2D Co(II)-Imidazole MOF as Cocatalyst and Ru(bpy)3 Cl2 as Photosensitizer.

The first application of an imidazole MOF, the 2D Co(II)- imidazole framework, {[Co(TIB)2 (H2 O)4 ]SO4 } (TIB stands for 1,3,5-tris(1-imidazolyl) benzene) (CoTIB) in photocatalytic CO2 reduction was carried out, and compared with that of ZIF-67. The CO2 /CoTIB (1.0 mg)/Ru(bpy)3 Cl2 (bpy=2,2'-bipyridine) (11.3 mg)/CH3 CN (40 mL)/TEOA (10 mL)/H2 O (400 μL) system produced 76.9 μmol of CO in 9 h, corresponding to the efficiency of 9.4 mmol g-1 h-1 (TOF: 7.3 h-1 ) with a >99% selectivity. Its catalytic activity is even higher than that of ZIF-67 based on TOF values. However, CoTIB is non-porous and has a very poor CO2 adsorption capacity and poor conductivity. Extensive photocatalytic experiments and energy-level diagrams suggest that the reduction did not depend on the CO2 adsorption by the cocatalyst, but can occur by the direct electron transfer from conduction-band maximum (CBM) of the cocatalyst to the zwitterionic alkylcarbonate adduct formed by the reaction of TEOA and CO2 . In addition, the process utilizes the short-lived singlet state (1 MLCT), not the long-lived triplet state (3 MLCT) of Ru(bpy)3 Cl2 to transfer electrons to the CBM of CoTIB. We found that the high efficiency of a cocatalyst, a photosensitizer, or a photocatalytic system depends on the matching of all related energy levels of the photosensitizer, the cocatalyst, CO2 , and the sacrificial agent in the reaction system.

Probing Charge-Transfer Processes in a Covalently Linked [Ge9 ]-Cluster Imine Dyad.

C60 donor dyads in which the carbon cage is covalently linked to an electron-donating unit have been discussed as one possibility for an electron-transfer system, and it has been shown that spherical [Ge9 ] cluster anions show a close relation to fullerenes with respect to their electronic structure. However, the optical properties of these clusters and of functionalized cluster derivatives are almost unknown. We now report on the synthesis of the intensely red [Ge9 ] cluster linked to an extended π-electron system. [Ge9 {Si(TMS)3 }2 {CH3 C=N}-DAB(II)Dipp ]- (1- ) is formed upon the reaction of [Ge9 {Si(TMS)3 }2 ]2- with bromo-diazaborole DAB(II)Dipp -Br in CH3 CN (TMS=trimethylsilyl; DAB(II)=1,3,2-diazaborole with an unsaturated backbone; Dipp=2,6-di-iso-propylphenyl). Reversible protonation of the imine entity in 1- yields the deep green, zwitterionic cluster [Ge9 {Si(TMS)3 }2 {CH3 C=N(H)}-DAB(II)Dipp ] (1-H) and vice versa. Optical spectroscopy combined with time-dependent density functional theory suggests a charge-transfer excitation between the cluster and the antibonding π* orbital of the imine moiety as the cause of the intense coloration. An absorption maximum of 1-H in the red region of the electromagnetic spectrum and the corresponding lowest-energy excited state at λ=669 nm make the compound an interesting starting point for further investigations targeting the design of photo-active cluster compounds.

1,4-Bis(trimethylsilyl)piperazine—Thermal Properties and Application as CVD Precursor

We report an investigation into 1,4-Bis-N,N-(trimethylsilyl)piperazine (BTMSP) as a novel precursor for the synthesis of silicon carbonitride films by chemical vapor deposition (CVD). The thermal stability, temperature dependence of vapor pressure and thermodynamic constants of the evaporation process of BTMSP were determined by static tensimetry with a glass membrane zero manometer. The transformation of the compound in low-power (25 W) plasma conditions was investigated by optical emission spectroscopy. It was shown that BTMSP undergoes destruction, accompanied by H and CH elimination and CN formation. SiCN(H) films were deposited in a hot-wall plasma-enhanced CVD reactor. The optical properties of the films were studied by spectral ellipsometry (refractive index: 1.5–2.2; absorption coefficient: 0–0.12) and UV–Vis spectroscopy (transmittance: up to 95%; optical bandgap: 1.6–4.9 eV). Information on the aging behavior of the films is also provided. The transformation of the films occurred through water adsorption and the formation of Si–O bonds with the degradation of Si–H, N–H and Si–CHx–Si bonds.

Automated solid-phase synthesis of metabolically stabilized triazolo-peptidomimetics.

The use of 1,4-disubstituted 1,2,3-triazoles as trans-amide bond surrogates has become an important tool for the synthesis of metabolically stabilized peptidomimetics. These heterocyclic bioisosters are generally incorporated into the peptide backbone by applying a diazo-transfer reaction followed by CuAAC (click chemistry) with an α-amino alkyne. Even though the manual synthesis of backbone-modified triazolo-peptidomimetics has been reported by us and others, no procedure has yet been described for an automated synthesis using peptide synthesizers. In order to efficiently adapt these reactions to an automated setup, different conditions were explored, putting special emphasis on the required long-term stability of both the diazo-transfer reagent and the Cu(I) catalyst in solution. ISA·HCl is the reagent of choice to accomplish the diazo-transfer reaction; however, it was found instable in DMF, the most commonly used solvent for SPPS. Thus, an aqueous solution of ISA·HCl was used to prevent its degradation over time, and the composition in the final diazo-transfer reaction was adjusted to preserve suitable swelling conditions of the resins applied. The CuAAC reaction was performed without difficulties using [Cu (CH3 CN)4 ]PF6 as a catalyst and TBTA as a stabilizer to prevent oxidation to Cu(II). The optimized automated two-step procedure was applied to the synthesis of structurally diverse triazolo-peptidomimetics to demonstrate the versatility of the developed methodology. Under the optimized conditions, five triazolo-peptidomimetics (8-5 amino acid residues) were synthesized efficiently using two different resins. Analysis of the crude products by HPLC-MS revealed moderate to good purities of the desired triazolo-peptidomimetics (70-85%). The synthesis time ranged between 9 and 12.5h.

Cooperativity-Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex.

In this report, we present the dinuclear copper(II) dimethylglyoxime (H2 dmg) complex [Cu2 (H2 dmg)(Hdmg)(dmg)]+ (1), which, in contrast to its mononuclear analogue [Cu(Hdmg)2 ] (2), is subject to a cooperativity-driven hydrolysis. The combined Lewis acidity of both copper centers increases the electrophilicity of the carbon atom in the bridging μ2 -O-N=C-group of H2 dmg and thus, facilitates the nucleophilic attack of H2 O. This hydrolysis yields butane-2,3-dione monoxime (3) and NH2 OH that, depending on the solvent, is then either oxidized or reduced. In ethanol, NH2 OH is reduced to NH4 + , yielding acetaldehyde as the oxidation product. In contrast, in CH3 CN, NH2 OH is oxidized by CuII to form N2 O and [Cu(CH3 CN)4 ]+ . Herein are presented the combined synthetic, theoretical, spectroscopic and spectrometric methods that indicate and establish the reaction pathway of this solvent-dependent reaction.

ReH3 (PPh3 )4 ] - A Key Compound in the Rhenium Hydride Chemistry.

The chemistry of the rhenium trihydrido complex [ReH3 (PPh3 )4 ] (1) has been reinvestigated. An improved synthesis and the solid-state structure of the compound as well as several reactions are reported. The solid-state structure of 1 is similar to that of [TcH3 (PPh3 )4 ] having a capped-octahedral coordination sphere. The PPh3 ligands surround the Re atom in a trigonal-pyramidal mode with a short apical Re-P bond (2.300(2) Å) and three longer basal bonds (2.429(2)-2.449(2) Å). Reactions of 1 with monodentate phosphines such as PMe3 or PBu3 give the mono-substituted complexes [ReH3 (PPh3 )3 (PMe3 )] (2) and [ReH3 (PPh3 )3 (PBu3 )] (3) under retention of the apical PPh3 ligand and substitution of one of the basal PPh3 ligands. The stability of the phosphine trihydride complexes decreases in the order PPh3 >PMe3 >PBu3 . Treatment of [ReH3 (PPh3 )4 ] with trityl hexafluorophosphate in CH3 CN does not result in a hydride abstraction, but gives the tetrahydrido cation [ReH4 (NCCH3 )(PPh3 )3 ]+ (4), while reactions with nitriles give unstable azavinylidene complexes of the composition [ReH2 (PPh3 )3 (NC(H)R)] (5). They are formed by an insertion of the nitrile into a Re-H bond. The solid-state structure of the methyl derivative [ReH2 (PPh3 )3 (NC(H)CH3 )] (5 a) was determined showing a linear Re-N-C unit with rhenium-nitrogen and nitrogen-carbon double bonds, while the N=CH-C bond is clearly bent with an angle of 124°. Two previously unknown polymorphs of [ReH5 (PPh3 )3 ] were isolated from reactions of 1 with HOC6 H3 (CH3 )2 and thiourea after prolonged heating in toluene and characterized by IR spectroscopy and X-ray diffraction.

Cycloisomerization of Alkyne-Tethered N-Acyloxycarbamates to 2-(3H)Oxazolones through Nitrenoid-Mediated Carboxyamidation.

The cycloisomerization of alkyne-tethered N-benzoyloxycarbamates to 2-(3H)oxazolones is described. Two catalytic systems are tailored for intramolecular 5-exo-alkyne carboxyamidation and concomitant alkene isomerization. PtCl2 /CO (5 mol%, toluene, 100 °C) promotes both carboxyamidation and alkene isomerization but has a limited substrate scope. On the other hand, FeCl3 (5 mol%, CH3 CN, 100 °C) promotes carboxyamidation effectively but a cocatalyst is required for the exocyclic alkene isomerization. Thus, a two-step one-pot protocol has been developed for a broader reaction scope, which involves FeCl3 -catalyzed carboxyamidation and base-induced alkene isomerization. Crossover experiments suggest that these reactions proceed mainly through a mechanism involving acylnitrenoid intermediates rather than carbenoid intermediates.

Spin Crossover Induced by Changing the Identity of the Secondary Metal Ion from PdII to NiII in a Face-Centered FeII 8 MII 6 Cubic Cage.

Discrete spin crossover (SCO) heteronuclear cages are a rare class of materials which have potential use in next-generation molecular transport and catalysis. Previous investigations of cubic cage [Fe8 Pd6 L8 ]28+ constructed using semi-rigid metalloligands, found that FeII centers of the cage did not undergo spin transition. In this work, substitution of the secondary metal center at the face of the cage resulted in SCO behavior, evidenced by magnetic susceptibility, Mössbauer spectroscopy and single crystal X-ray diffraction. Structural comparisons of these two cages shed light on the possible interplay of inter- and intramolecular interactions associated with SCO in the NiII analogue, 1 ([Fe8 Ni6 L8 (CH3 CN)12 ]28+ ). The distorted octahedral coordination environment, as well as the occupation of the CH3 CN in the NiII axial positions of 1, prevented close packing of cages observed in the PdII analogue. This led to offset, distant packing arrangements whereby important areas within the cage underwent dramatic structural changes with the exhibition of SCO.

Discriminating alkylbenzene isomers with tandem mass spectrometry using a dielectric barrier discharge ionization source.

Soft ambient ionization sources generate reactive species that interact with analyte molecules to form intact molecular ions, which allows rapid, sensitive, and direct identification of the molecular mass. We used a dielectric barrier discharge ionization (DBDI) source with nitrogen at atmospheric pressure to detect alkylated aromatic hydrocarbon isomers (C8 H10 or C9 H12 ). Intact molecular ions [M]•+ were detected at 2.4kVpp , but at increased voltage (3.4 kVpp ), [M + N]+ ions were formed, which could be used to differentiate regioisomers by collision-induced dissociation (CID). At 2.4 kVpp , alkylbenzene isomers with different alkyl-substituents could be identified by additional product ions: ethylbenzene and -toluene formed [M-2H]+ , isopropylbenzene formed abundant [M-H]+ , and propylbenzene formed abundant C7 H7 + . At an operating voltage of 3.4 kVpp , fragmentation of [M + N]+ by CID led to neutral loss of HCN and CH3 CN, which corresponded to steric hindrance for excited state N-atoms approaching the aromatic ring (C-H). The ratio of HCN to CH3 N loss (interday relative standard deviation [RSD]< 20%) was distinct for ethylbenzene and ethyltoluene isomers. The greater the number of alkyl-substituents (C-CH3 ) and the more sterically hindered (meta > para > ortho) the aromatic core, the greater the loss of CH3 CN relative to HCN was.

Multiple Stellar Populations of Globular Clusters from Homogeneous Ca–CN–CH–NH Photometry. VII. Metal-poor Populations in 47 Tucanae (NGC 104)* * Based on observations made with the Cerro Tololo Inter-American Observatory (CTIO) 1 m telescope, which is operated by the SMARTS consortium. † †This work presents results from the European Space Agency space mission Gaia. Gaia data are being processed by the

We present new large field-of-view (∼1°×1°) Ca-CN photometry of the prototypical metal-rich globular cluster 47 Tucanae (NGC 104). Our results are the following. (1) The populational number ratios of the red giant branch (RGB) and red horizontal branch (RHB) are in excellent agreement: n(CN-w):n(CN-s) = 30:70 (±1–2), where the CN-w and CN-s stand for the CN-weak and CN-strong populations, respectively. Both the CN-s RGB and RHB populations are more centrally concentrated than those of CN-w populations are. (2) Our photometric metallicities of individual RGB stars in each population can be well described by bimodal distributions with two metallicity peaks, [Fe/H] ∼−0.72 and −0.92 dex, where the metal-poor components occupy ∼13% of the total RGB stars. The metal-poor populations are more significantly centrally concentrated than the metal-rich populations, showing a similar result that we found in M3. (3) The RGB bump V magnitudes of individual populations indicate that there is no difference in the helium abundance between the two metal-poor populations, while the helium enhancement of ΔY ∼0.02–0.03 is required between the the two metal-rich populations. (4) The RHB morphology of 47 Tuc appears to support our idea of the bimodal metallicity distribution of the cluster. We suggest that 47 Tuc could be another example of merger remnants of two globular clusters, similar to M3 and M22.

Polyphosphazene-Functionalized Microspheres as Efficient Catalysts for the Knoevenagel Reaction under Mild Conditions.

Inspired by the formation of microspheres by hexachlorocyclotriphosphazene and 4, 4'-sulfonyldiphenol, polyphosphazene-functionalized microspheres were developed. Benefits from the supported supper basic phosphazene, the yield exceeded 99 % at room temperature in the manner of second-order reaction kinetics toward Knoevenagel reaction and was still maintained at 99 % after 16 runs. In the experimental temperature from 0 °C to 90 °C, the yield increased from 92 % to 99 %, reflecting that the catalyst had strong applicability under mild conditions. This behavior was conducive to energy conservation. Meanwhile, simple separation and recovery further enhanced this advantage. In addition, the catalyst was also found to be insensitive to aqueous solution or organic solvents such as toluene, THF, EtOH and CH3 CN. This property gave the Knoevenagel reaction a vast choice. All these features exhibit that this novel catalyst is an attractive and applicable alternative in organic synthesis.

Treatment of bromate in UV/sulfite autoxidation process enhances formation of dibromoacetonitrile during chlorination

The integration of UV/sulfite autoxidation process (USAP, i.e., UV activation of sulfite in the presence of 5 ∼ 10 mg/L O2) into conventional water to degrade micropollutants rises extensive attention, but its impact on water quality, and especially the formation of disinfection byproducts is still unclear. Herein, the formation of dibromoacetonitrile (DBAN) from bromate (BrO3–) upon treatment with USAP followed by chlorination was evaluated, in the presence of amino acids (AAs) selected as representative organic matter in drinking water. Results revealed that hydrated electrons (eaq–) produced during USAP contribute to the reduction of BrO3– to Br–, which is then converted into HBrO/BrO– during post-chlorination. At the same time, sulfate radicals (SO4•–) and hydroxyl radicals (•OH) generated in USAP mediated AAs’ conversion via α-hydrogen abstraction and NH2-hydrogen abstraction reactions to produce HN=C(CH3)‒COOH, CH3‒CH=NH, and CH3‒CN, which are released into the post-chlorination stage and therefore, enhance the bromine utilization factor (BUF) value and DBAN formation. The effects of the USAP treatment time, BrO3– concentration, AA concentration, pH, and real waters were also evaluated. Although 63.5% of BrO3– was eliminated by USAP followed by chlorination, the toxicity index (TI) was increased by 1.5-fold due to the formation of the all brominated CX3R-type nitrogenous disinfection byproducts (N-DBPs), demonstrating the potential risk of applying USAP as a treatment process in BrO3– containing waters.

Formation and Reactivity of a Fleeting NiIII Bisphenoxyl Diradical Species.

Cytochrome P450s and Galactose Oxidases exploit redox active ligands to form reactive high valent intermediates for oxidation reactions. This strategy works well for the late 3d metals where accessing high valent states is rather challenging. Herein, we report the oxidation of NiII (salen) (salen=N,N'-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with mCPBA (meta-chloroperoxybenzoic acid) to form a fleeting NiIII bisphenoxyl diradical species, in CH3 CN and CH2 Cl2 at -40 °C. Electrochemical and spectroscopic analyses using UV/Vis, EPR, and resonance Raman spectroscopies revealed oxidation events both on the ligand and the metal centre to yield a NiIII bisphenoxyl diradical species. DFT calculations found the electronic structure of the ligand and the d-configuration of the metal center to be consistent with a NiIII bisphenoxyl diradical species. This three electron oxidized species can perform hydrogen atom abstraction and oxygen atom transfer reactions.

Infrared spectra of complex organic molecules in astronomically relevant ice mixtures

Context. The increasing sensitivity and resolution of ground-based telescopes have enabled the detection of gas-phase complex organic molecules (COMs) across a variety of environments. Many of the detected species are expected to form on the icy surface of interstellar grains and transfer later into the gas phase. Therefore, icy material is regarded as a primordial source of complex molecules in the interstellar medium. Upcoming James Webb Space Telescope (JWST) observations of interstellar ices in star-forming regions will reveal infrared (IR) features of frozen molecules with unprecedented resolution and sensitivity. To identify COM features in the JWST data, laboratory IR spectra of ices for conditions that simulate interstellar environments are needed. Aims. This work provides laboratory mid-IR spectra of methyl cyanide (CH3CN, also known as acetonitrile) ice in its pure form and mixed with known interstellar molecules at cryogenic temperatures. The spectroscopic data presented in this work will support the interpretation of JWST ice observations and are made available to the community through the Leiden Ice Database for Astrochemistry (LIDA). Methods. Fourier transform IR spectroscopy is used to record the mid-IR spectra (500–4000 cm−1/20–2.5 µm, with a resolution of 1 cm−1 ) of methyl cyanide (acetonitrile, CH3 CN) mixed with H2O, CO, CO2, CH4, NH3, H2O:CO2, and H2O:CH4:NH3, at temperatures ranging from 15 to 150 K. The refractive index (at 632.8 nm) of pure amorphous CH3CN ice at 15 K and the band strength of selected IR transitions are also measured. Results. We present a variety of reference mid-IR spectra of frozen CH3CN that can be compared to astronomical ice observations. The peak position and full width at half maximum (FWHM) of six absorption bands of frozen methyl cyanide in its pure form and mixed ices, at temperatures between 15–150 K, are characterized. These bands are the following: the CH3 symmetric stretching at 2940.9 cm−1 (3.400 µm), the CN stretching at 2252.2 cm−1 (4.440 µm), a peak resulting from a combination of different vibrational modes at 1448.3 cm−1 (6.905 µm), the CH3 antisymmetric deformation at 1410 cm−1 (7.092 µm), the CH3 symmetric deformation at 1374.5 cm−1 (7.275 um), and the CH3 rock vibration at 1041.6 cm−1 (9.600 um). Additionally, the apparent band strength of these vibrational modes in mixed ices is derived. The laboratory spectra of CH3CN are compared to observations of interstellar ices toward W33A and three low-mass Young Stellar Objects (YSO). Since an unambiguous identification of solid methyl cyanide toward these objects is not possible, upper limits for the CH3CN column density are determined as ≤2.4 × 1017 molecules cm−2 for W33A and 5.2 × 1016, 1.9 × 1017, and 3.8 × 1016 molecules cm−2 for EC92, IRAS 03235, and L1455 IRS3, respectively. With respect to solid H2O, these values correspond to relative abundances of 1.9, 3.1, 1.3, and 4.1%, for W33A, EC92, IRAS 03235, and L1455 IRS3, respectively.