Oxide Fluoride Research Articles

РЕНТГЕНОЛЮМИНЕСЦЕНТНЫЕ КОМПОЗИТЫ НА ОСНОВЕ ПОЛИКРИСТАЛЛИЧЕСКОГО АЛМАЗА С ИНТЕГРИРОВАННЫМИ НАНОЧАСТИЦАМИ NaGdF4:Eu ДЛЯ ФОТОНИКИ

Разработаны люминесцентные алмазные композиты c интегрированными наночастицами β-NaGdF4:Eu, обладающие высокоинтенсивной узкополосной рентгенолюминесценцией на длине волны 612 нм. Отмечена концентрационная зависимость интенсивности рентгенолюминесценции от содержания частиц. Использование нанопорошков β-NaGdF4:Eu позволило получить интенсивную рентгенолюминесценцию с более высоким соотношением сигнал/шум, нежели было достигнуто ранее.
 
 Работа выполнена при финансовой поддержке гранта РФФИ № 16-29-11784-офи.
 Результаты получены с использованием оборудования центров коллективного пользования ИОФ РАН и ИОНХ РАН.

An Asymmetric Anion‐Pillared Metal–Organic Framework as a Multisite Adsorbent Enables Simultaneous Removal of Propyne and Propadiene from Propylene

AbstractThe one‐step removal of multi‐component gases based on a single material will significantly improve the efficiency of separation processes but it is challenging, owing to the difficulty to precisely fabricate porous materials with multiple binding sites tailored for different guest molecules. Now a niobium oxide–fluoride anion‐pillared interpenetrated material ZU‐62 (NbOFFIVE‐2‐Cu‐i, NbOFFIVE=NbOF52−) is presented. It features asymmetric O/F node coordination for the simultaneous removal of trace propyne and propadiene from propylene. The narrow distribution nanospace (aperture of Site I 6.75 Å, Site II 6.94 Å, Site III 7.20 Å) derived from the special coordination geometry within ZU‐62 customized the corresponding energy‐favorable binding sites for the propyne and propadiene that enable propadiene uptake (1.74 mmol g−1) as well as excellent propyne uptake (1.87 mmol g−1) under ultra‐low pressure (5000 ppm). The multisite capture mechanism was revealed by modeling studies.

Theoretical prediction of two-dimensional CrOF sheet as a ferromagnetic semiconductor or a half-metal

Two-dimensional chromium oxide fluoride CrOF sheet was studied based on density functional theory. The investigation indicates that the CrOF sheet is an intrinsic ferromagnetic semiconductor. The corresponding Curie temperature is 150 K. In particular, the Curie temperature increases up to 410 K under hole doping and the CrOF sheet becomes a half-metal. The versatile electronic and magnetic properties indicate that the two-dimensional CrOF sheet can be a promising candidate for next-generation spintronic devices.

Making an order: the concerted alignment of [MOF5]2- (M = Nb and Ta) dipolar anions in one-dimensional coordination chains sustained by tris(3,4,5-trimethyl-1H-pyrazole)copper(II).

Electronic distortions, which are inherent in the oxide fluoride anions [MOF5]2- (M = Nb and Ta), provide an origin of polar molecular arrangements for the development of new polar second-harmonic-generating, piezo-, pyro- and ferroelectric materials. It is still a challenge to expand this approach to the realm of metal-organic polymers, while insufficient control over the environment of the [MOF5]2- units results in their orientational disorder and loss of polarity. The structures of catena-poly[[tris(3,4,5-trimethyl-1H-pyrazole-κN2)copper(II)]-μ-oxido-[tetrafluoridoniobium(V)]-μ-fluorido], [CuNbF5O(C6H10N2)3]n, (I), and its isostructural pentafluoridooxidotantalate(V) analogue, catena-poly[[tris(3,4,5-trimethyl-1H-pyrazole-κN2)copper(II)]-μ-oxido-[tetrafluoridotantalum(V)]-μ-fluorido], [CuTaF5O(C6H10N2)3]n, (II), are the first examples of the strict orientational order of [MOF5]2- (M = Nb and Ta) in one-dimensional coordination chains. A primary factor for the exact discrimination of one orientation of the anion over the other is strong and shape-selective multiple interactions of [MOF5]2- with the inherently acentric CuL32+ platform, with a set of two coordination and three N-H...F hydrogen bonds. In (I) and (II), the Cu2+ ions exhibit distorted square-pyramidal fivefold coordination formed by three pyrazole N atoms and the oxide O atom, defining the equatorial plane, and the anionic bridging F atom (which is trans with respect to the M-O bond) residing in the apical position. The inorganic bridges connect CuL32+ moieties into polar zigzag chains; the bulk polarity of the structure is eliminated by an antiparallel alignment of the individual chains. These chains are further connected through C-H...F hydrogen bonding and very weak C-H...π interactions of the organic ligands.

Influence of Nonstoichiometry in Fluoride Phase on the Ionic Conductivity of Composite Fluoride‒Oxide Materials 90PrF3 · 10Al2O3 and 90Pr0.95Sr0.05F2.95 · 10Al2O3

The two-phase fluoride oxide composite 90Pr0.95Sr0.05F2.95 · 10Al2O3 (mol %) composed of a highly conductive fluoride matrix with a tysonite structure (LaF3) and aluminium oxide is of interest as a solid electrolyte membrane in a potentiometric oxygen sensor with an auxiliary electrode. The ionic conductivity of the composite 90Pr0.95Sr0.05F2.95 · 10Al2O3 has been determined by impedance spectroscopy in vacuum (~0.1 Pa) in the temperature range of 293‒700 K. Its dominant component is the conducting non-stoichiometric tysonite phase Pr0.95Sr0.05F2.95. To estimate the contribution of this phase to the composite conductivity, the conductivities of the single-phase (single-crystal) PrF3 and Pr0.95Sr0.05F2.95 bases and a twophase composite 90PrF3 · 10Al2O3 with a stoichiometric fluoride matrix PrF3 have been investigated. The use of the nonstoichiometric phase Pr0.95Sr0.05F2.95 as a composite matrix instead of PrF3 leads to an improvement of ionic conductivity by a factor of ~200: to 5 × 10–3 S/cm at 400°C.

Nollmotzite, Mg[UV(UVIO2)2O4F3]·4H2O, the first natural uranium oxide containing fluorine.

Nollmotzite (IMA2017-100), Mg[UV(UVIO2)2F3O4](H2O)4, is a new uranium oxide fluoride mineral found in the Clara mine, Black Forest Mountains, Germany. Electron microprobe analysis provided the empirical formula (Mg1.06Cu0.02)Σ1.08[UV(UVIO2)2O3.85F3.15][(H2O)3.69(OH)0.31]Σ4.00 based on three U and 15 O + F atoms per formula unit. Nollmotzite is monoclinic, space group Cm, with a = 7.1015 (12) Å, b = 11.7489 (17) Å, c = 8.1954 (14) Å, β = 98.087 (14)°, V = 676.98 (19) Å3 and Z = 2. The crystal structure [twinned by reticular merohedry; refined to R = 0.0369 with GoF = 1.09 for 1527 unique observed reflections, I > 3σ(I)] is based upon [UV(UVIO2)2F3O4]2- sheets of β-U3O8 topology and contains an interlayer with MgF2(H2O)4 octahedra. Adjacent sheets are linked through F-Mg-F bonds, as well as via hydrogen bonds. The presence of fluorine and pentavalent uranium in the structure of nollmotzite has potentially important implications for the safe disposal of nuclear waste.

Kinetic Studies on the Thermal Synthesis of Fluorapatite: Model Free and Model-Fitting Methods

The kinetic study for the synthesis of Fluorapatite has been done using the thermogravimetric technique under non-isothermal conditions and at four heating rates of 5, 10, 15 and 20 °C. Both model free and model-fitting methods were used to investigate kinetic parameters. Calcium oxide, phosphorus pentoxide and calcium fluoride were used as the precursor materials. The activation energy values were calculated through model-fitting and isoconversional methods and were used to predict the reaction model and pre-exponential factor. In this case several techniques were considered such as master plots and compensation effects. The results indicated that the reaction mechanism was chemically controlled with second and third order reaction models in the whole range of conversion which the activation energy varied from 25 to 43 kJ/mol.

Fabrication and Characterization of Manganese‐based Self‐assembled Cubic Structures

AbstractSelf‐assembled cubic structures of manganese‐based nanomaterials were achieved successfully, in case of manganese fluoride, for the very first time. The indirect synthesis of manganese oxide (Mn2O3) and manganese fluoride (MnF2/MnF3) self‐assembly involved an individual two step synthesis protocol. In first step of the protocol, NH4MnF3 self‐assembled cubic structures were fabricated by a simple liquid phase reaction using polystyrene (PS) as structure directing agent (SDA), while manganese nitrate tetrahydrate (Mn(NO3)2.4H2O) and ammonium fluoride (NH4F) as manganese and fluorine sources, respectively. In second step, the NH4MnF3 was transformed by calcination to manganese oxide (Mn2O3) at 450 °C for 5 hours under open atmosphere (air/O2), and individually, to manganese fluoride (MnF2/MnF3) at 350 °C for 5 hours under pure molecular fluorine (F2) environment. The temperature regimes for the transformation reactions were deduced from thermogravimetric analysis (TGA). The crystal structures and the compositions of all the samples were established by powder X‐rays diffraction (PXRD). Further, structural characterizations were carried out by spectroscopic analyses. The key objective, preservation of self‐assembled cubic structures in the resulting manganese oxide and fluoride, were confirmed by electron microscopic analyses. The self‐assembly structures formation mechanism was illustrated based on the transmission electron microscopy (TEM) and scanning electron microscopy (SEM) results.

Enhanced electrochemical properties of the Cd-modified LiNi0.6Co0.2Mn0.2O2 cathode materials at high cut-off voltage

High voltage property applied in cells is one of the critical directions for high energy density lithium-ion battery. In this work, cadmium oxides are used as the modifying material on the LiNi0.6Co0.2Mn0.2O2 cathode materials by a facile chemical precipitation method followed by post-calcination. The cadmium oxides not only cover on the LiNi0.6Co0.2Mn0.2O2 particles surface homogenously, but also diffuse into the crystal lattice of the LiNi0.6Co0.2Mn0.2O2 with gradient distribution. The formed cadmium oxide and metal fluorides mixed-layer during cycling on the surface makes the interfacial stability significantly improved. Therefore, the side-reactions are suppressed effectively. The gradient doping of the cadmium in the crystal lattice enhances the structural stability of the LiNi0.6Co0.2Mn0.2O2 and facilitates the Li+ and electron transportation in the bulk material. Moreover, the residual lithium components (Li2CO3/LiOH) also decrease significantly. As a result, the obtained Cd-modified LiNi0.6Co0.2Mn0.2O2 cathodes rise 16.60 (100 cycles, 3.0–4.6 V) and 13.87 (200 cycles, 3.0–4.5 V) percentage points at 1 C rate, respectively. The initial capacity of cadmium-modified LiNi0.6Co0.2Mn0.2O2 is 160.8 mAh g−1 at 8 C rate over 3.0–4.5 V. The proposed cadmium oxide modification may be also potentially applied in other active cathode materials, especially for the high voltage performance.

Assisting the Effective Design of Polar Iodates with Early Transition-Metal Oxide Fluoride Anions.

Polar materials are of great technical interest but challenging to effectively synthesize. That is especially true for iodates, an important class of visible and mid-IR transparent nonlinear optical (NLO) materials. Aiming at developing a new design strategy for polar iodates, we successfully synthesized two sets of polymorphic early transition-metal (ETM) oxide-fluoride iodates, α- and β-Ba[VFO2(IO3)2] and α- and β-Ba2[VO2F2(IO3)2]IO3, based on the distinct structure-directing properties of oxide-fluoride anions. α- and β-Ba[VFO2(IO3)2] contain the trans-[VFO2(IO3)2]2- polyanion and crystallize in the nonpolar space groups Pbcn and P212121. In contrast, α- and β-Ba2[VO2F2(IO3)2]IO3 contain the cis-[VO2F2(IO3)2]3- Λ-shaped polyanion and crystallize in the polar space groups Pna21 and P21, respectively. Detailed structural analyses show that the variable polar orientation of trans-[VFO2(IO3)2]2- polyanions is the main cause of the nonpolar structures in α- and β-Ba[VFO2(IO3)2]. However, the Λ-shaped configuration of cis-[VO2F2(IO3)2]3- polyanions can effectively guarantee the polar structures. Further property measurements show that polar α- and β-Ba2[VO2F2(IO3)2]IO3 possess excellent NLO properties, including the large SHG responses (∼9 × KDP), wide visible and mid-IR transparent region (∼0.5-10.5 μm), and high thermal stability (up to 470 °C). Therefore, combining cis-directing oxide-fluoride anions and iodates is a viable strategy for the effective design of polar iodates.

Synthesis, characterization of reduced graphene oxide nanosheets and its reinforcement effect on polymer electrolyte for dye sensitized solar cell applications

High performance polymer electrolyte for dye sensitized solar cell application has been prepared using suitable polymer matrix reinforced by reduced graphene oxide (RGO) nanosheets. RGO nanosheet has been synthesized using appropriately modified Hummer’s method. The matrix has been formulized as an optimized blend of polyethylene oxide and polyvinylidene fluoride – hexafluoro propylene (PEO/PVDF-HFP) to get expected high performance characteristics in terms of ionic conductivity, charge carrier concentration and diffusion coefficient. The same has been confirmed using electrochemical impedance spectroscopy and linear steady state voltammetry. Excellent stability of the electrolyte also has been recorded through efficiency retention study. Further, solar cell has been fabricated using the optimized formulation of PEO/PVDF-HFP/RGO nanosheet polymer electrolyte. The optimum performance in comparison with liquid electrolyte based solar cell has been authorized through photo voltaic performance study in terms of open circuit voltage (Voc), short circuit current (Jsc) and solar conversion efficiency.

High-resolution flexible temperature sensor based graphite-filled polyethylene oxide and polyvinylidene fluoride composites for body temperature monitoring

Flexible and high accurate temperature sensors have great potential toward applications such as medical diagnosis and body temperature monitoring. Here, we demonstrated a flexible temperature sensor based on graphite-filled polyethylene oxide (PEO) and polyvinylidene fluoride (PVDF) composites exhibiting a high accuracy of 0.1 °C and high repeatability nearly 2000 times, in the sensing temperature range of 25–42 °C. Device performance is hardly affected in different curvature, which allows for conformal application to human skin. Especially, subtle temperature change on the skin surface was also measured to validate the accuracy and anti-interference ability. Under physiological conditions, the temperature sensor based on positive temperature coefficient showed a high-speed response time of 26 s with relatively simple fabrication technology. These results demonstrated the possibility and feasibility of fully using the sensors in body temperature sensing for medical use as well as sensing function of body temperature measuring.

Fabrication of Li-Polymer/Silica Aerogel Nanocomposite Electrolyte for an All-Solid-State Lithium Battery

The demand for solid-state lithium ion electrolytes has increased owing to the safety concerns regarding the use of lithium ion batteries, which contain flammable organic solvent electrolytes. The liquid electrolyte can give rise to serious problems such as leakage and gas explosions when the operating temperature rises. The use of an organic or inorganic solid electrolyte not only results in improved safety, but also facilitates the fabrication of miniature batteries using thin films. A solid electrolyte is required to have high lithium ion conductivity, mechanical strength, and transference number for lithium ions as well as good thermal/electrochemical stability and compatibility with the electrodes. Recently, polymer-based solid electrolytes have been widely studied for a possible replacement for liquid electrolytes. Various types of polymer-based solid electrolytes for lithium ion batteries exist, such as polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), and polyvinylidene fluoride (PVDF). Among them, the PEO-based polymer has attracted considerable attention, owing to its flexible skeleton and good interfacial stability with lithium electrodes. The mechanism of lithium ion conduction in the PEO-based solid-polymer electrolyte involves the coordination of the lithium ion from the Li-salt by the ether oxygen from the PEO, which moves according to the polymer segmental motion. In this study, a polymer blend of PEO and PVDF, containing fluorine as a polar element, was fabricated to improve the dissociation degree of the Li-salt. In addition, we anticipate that the addition of ultra-porous silica aerogels, which has a high porosity and specific surface area, would increase the lithium ion conductivity. The silica aerogel was fabricated from water glass using the emulsion polymerization method, as was previously described by our research group. We also investigated the effects of the PEO:PVDF molar ratio, polymer:Li-salt molar ratio, and silica aerogel content on the structural, thermal, and electrical properties.

Glycerol dehydration to hydroxyacetone in gas phase over copper supported on magnesium oxide (hydroxide) fluoride catalysts

The dehydration of glycerol to hydroxyacetone was studied over copper-based catalysts using magnesium oxide (hydroxide) fluoride with various F/Mg ratio as support of copper. After calcination at 350 °C, the incorporation of copper, mainly at + II oxidation state, into the support lattice was observed for MgO and MgF(OH) while, copper was stabilized as Cu+1 at the surface of Cu-MgF2. The reaction of dehydration was performed using a mixture of glycerol and water (80%wt of glycerol), in gas phase at 260 °C. Cu-MgF2 was the most active catalyst with a yield in hydroxyacetone of 45.5%, while the catalytic activity was very low for Cu-MgF(OH) and Cu-MgO (yield in HA < 10%). Moreover, the performances obtained for Cu-MgF2 were higher than those obtained with La2CuO4, a reference catalyst. After four hours of reaction, Cu-MgF2 was not significantly modified, while for the two other catalysts, Cu2+ initially present was reduced into metallic copper. The results obtained revealed that the basic properties of the catalysts did not govern the reaction of dehydration of glycerol into HA. The best catalyst (Cu-MgF2) was the one possessing the higher amount of Lewis acid sites, and stabilizing copper at + 1 oxidation state.

Extraction of Scandium and Zirconium from Their Oxides during the Electrolysis of Oxide–Fluoride Melts

The main features of scandium and zirconium extraction from their oxides to aluminum during the aluminothermic and electrolytic preparation of Al–Sc and Al–Zr alloys and master alloys in the KF–AlF3, NaF–AlF3, and KF–NaF–AlF3 oxide–fluoride melts with Sc2O3 and ZrO2 additives are studied. The influence of the melt composition and temperature, the synthesis time, the contents of oxides Sc2O3 and ZrO2 in the melts, the mechanical stirring of aluminum, and the cathodic current density on the contents of scandium and zirconium in aluminum and on their extraction from the oxides is determined. The average values of scandium and zirconium extraction are 20–75 and 40–100%, respectively, depending on the synthesis parameters. The electrolytic decomposition of the oxides in the KF–AlF3, NaF–AlF3, and KF–NaF–AlF3 melts results in the enhancement of scandium and zirconium extraction to aluminum. The parameters of the preparation of Al–Sc and Al–Zr alloys and master alloys with the scandium content to 10 wt % and zirconium content to 15 wt % during the electrolysis of oxide–fluoride melts are chosen as a result of the results obtained.

Tunable Self-Assembly of YF3 Nanoparticles by Citrate-Mediated Ionic Bridges.

Ligand-to-surface interactions are critical factors in surface and interface chemistry to control the mechanisms governing nanostructured colloidal suspensions. In particular, molecules containing carboxylate moieties (such as citrate anions) have been extensively investigated to stabilize metal, metal oxide, and metal fluoride nanoparticles. Using YF3 nanoparticles as a model system, we show here the self-assembly of citrate-stabilized nanostructures (supraparticles) with a size tunable by temperature. Results from several experimental techniques and molecular dynamics simulations show that the self-assembly of nanoparticles into supraparticles is due to ionic bridges between different nanoparticles. These interactions were caused by cations (e.g., ammonium) strongly adsorbed onto the nanoparticle surface that also interact strongly with nonbonded citrate anions, creating ionic bridges in solution between nanoparticles. Experimentally, we observe self-assembly of nanoparticles into supraparticles at 25 and 100 °C. Interestingly, at high temperatures (100 °C), this citrate-bridge self-assembly mechanism is more efficient, giving rise to larger supraparticles. At low temperatures (5 °C), this mechanism is not observed, and nanoparticles remain stable. Molecular dynamics simulations show that the free energy of a single citrate bridge between nanoparticles in solution is much larger than the thermal energy and in fact is much larger than typical adsorption free energies of ions on colloids. Summarizing our experiments and simulations, we identify as key aspects of the self-assembly mechanism the requirement of NPs with a surface able to adsorb anions and cations and the presence of multidentate ions in solution. This indicates that this new ion-mediated self-assembly mechanism is not specific of YF3 and citrate anions, as supported by preliminary experimental results in other systems.

Understanding the quenching nature of Mn4+ in wide band gap inorganic compounds: design principles for Mn4+ phosphors with higher efficiency.

Mn4+ doped phosphors, as an alternative to rare-earth element doped phosphors, have attracted immense attention owing to their ultrahigh quantum efficiency of red emission for potential applications in high rendering white LEDs (light-emitting diodes). Their performance can be largely affected by quenching phenomena such as thermal quenching, concentration quenching and the quenching induced by some intrinsic/extrinsic defects. However, the quenching mechanisms due to the defect levels and host band are still incompletely understood. In this work, we carry out a comprehensive first-principles study on the underlying quenching mechanisms due to the defect levels of Mn4+ and other extrinsic/intrinsic defects, using the prototype oxide Y3Al5O12 (YAG), fluorides K2TiF6 (KTF) and ZnTiF6·6H2O (ZTF) as examples. From the comparison of the defect levels of Mn4+ with the host bands, we find that it is the very small energy difference between the defect levels of Mn4+ and the valence bands maximum (VBM) of YAG that causes the lower luminescence thermal stability of YAG:Mn4+, which we name as the hole-type thermal quenching mechanism. For the concentration quenching, it is nearly impossible for the Mn4+-Mn4+ pairs, previously considered as the main quenching centers, to appear in phosphors. A new quenching nature has been discussed. For the impurity ionic effects, the hole-type defects can largely stabilize the Mn ions in +4 states, thereby enhancing the emission intensity. These proposed mechanisms can offer deeper insights into the luminescence behavior of Mn4+ and a better practical understanding of the high photoluminescence quantum yield red phosphors by adjusting their chemical components.

THEORETICAL JUSTIFICATION AND DEVELOPMENT OF THE SLAG MODE FOR TREATMENT OF WHEEL STEEL ON THE INSTALLATION OF A BUCKET-OVEN WITH A PURPOSE TO REDUCE THE SPECIFIC ELECTRIC ENERGY

Purpose. Management of the formation of oxide fluoride slag at the stage of out-furnace treatment of the wheel metal. Methodology. Investigations of the energy technological regimes of out-of-furnace treatment of wheel steel were performed by analyzing the parameters of the basic metal processing technology at the ladle furnace. Results. The optimal input mode of the fluorspar is established when the ladle slag is formed at the ladle furnace installation. Scientific novelty. Analytical studies confirmed the absence in the structure of oxide fluoride slag structures containing fluorspar. Its role in the formation of ladle slag is defined as a depolymerization unit of spatial silica-oxygen groups and, as a consequence, an increase in the flowability of the melt while simultaneously increasing the oxidative potential of the slag. Practical significance. The results of the study determine the limits of the CaF2 content in the ladle slag and allow a 30–35% reduction in the power consumption during slag formation at the ladle furnace. Key words: Wheeled steel, electric arc furnace, metal intermediate, deoxidizing agents, alloying, slag-forming materials, fluorspar, ladle-furnace installation, energy saving.

Highly Symmetric AB2 Framework Related to Tridymite in the Disordered Nitridosilicate La24Sr14-7x[Si36N72](O1-xFx)14 (x = 0.489).

La24Sr14-7x[Si36N72](O1-xFx)14 with x = 0.489 was obtained as a microcrystalline product by metathesis at 1500 °C in a radio-frequency furnace starting from Si(NH)2, La(NH2)3, SrH2, LaF3, and CeF3. The structure of the new nitridosilicate oxide fluoride was determined by combining transmission electron microscopy (TEM) and single-crystal X-ray diffraction using a microfocused synchrotron beam. The structure model with pronounced disorder [P63/mmc, Z = 1, a = 16.2065(3), c = 9.4165(1) Å, R1(obs) = 0.0436] was confirmed by electron diffraction and aberration-corrected Z-contrast scanning TEM. The highly symmetric AB2 framework, which was theoretically predicted but not yet realized, consists of all-side vertex-sharing SiN4 tetrahedra that form channels along [001] filled with La, Sr, O, and F atoms. The connectivity pattern is related to that of tridymite. X-ray spectroscopy and bond-valence-sum calculations were further taken into account for assignment of the N, O, and F atoms.

Infrared Spectroscopic and Theoretical Studies on the OMF2 and OMF (M = Cr, Mo, W) Molecules in Solid Argon

Group 6 metal oxide fluoride molecules in the form of OMF2 and OMF (M = Cr, Mo, W) were prepared via the reactions of laser-ablated metal atoms and OF2 in excess argon. Product identifications were performed by using infrared spectroscopy, 18OF2 samples, and electronic structure calculations. Reactions of group 6 metal atoms and OF2 resulted in the formation of ternary OCrF2, OMoF2, and OWF2 molecules with C2v symmetry in which the tetravalent metal center is coordinated by one oxygen and two fluorine atoms. Both OCrF2 and OMoF2 are computed to possess triplet ground states, and a closed shell singlet is the ground state for OWF2. Triatomic OCrF, OMoF, and OWF molecules were also observed during sample deposition. All three molecules were computed to have a bent geometry and quartet ground state. A bonding analysis showed that the OMF2 molecules have highly ionic M-F bonds. 3OCrF2 and 3OMoF2 have an M-O double bond composed of a σ bond and a π bond. 1OWF2 has an M-O triple bond consisting of a σ bond, a π bond, and a highly delocalized O lone pair forming the other π bond. The M-O bonds in the OMF compounds have triple-bond character for all three metals.