MoCl Research Articles

Molecular layer deposition of polyhydroquinone thin films for Li‐ion battery applications

AbstractMany next‐generation materials for Li‐ion batteries are limited by material instabilities. To stabilize these materials, ultrathin, protective coatings are needed that conduct both lithium ions and electrons. Here, we demonstrate a hybrid chemistry combining molecular layer deposition (MLD) of trimethylaluminum (TMA) and p‐hydroquinone (HQ) with oxidative molecular layer deposition (oMLD) of molybdenum pentachloride (MoCl5) and HQ to enable vapor‐phase molecular layer growth of poly(p‐hydroquinone) (PHQ)—a mixed electron and lithium ion conducting polymer. We employ quartz crystal microbalance (QCM) studies to understand the chemical mechanism and demonstrate controlled linear growth with a 0.5 nm/cycle growth rate. Spectroscopic characterization indicates that this hybrid MLD/oMLD chemistry polymerizes surface HQ monomers from the TMA‐HQ chemistry to produce PHQ. The polymerization to PHQ improves air stability over MLD TMA‐HQ films without crosslinking. Electrochemical measurements on hybrid MLD/oMLD films indicate electronic conductivity of ~10−9 S/cm and a Li‐ion conductivity of ~10−4 S/cm. While these coatings show promise for Li‐ion battery applications, this work focuses on establishing the coating chemistry and future studies are needed to examine the stability, structure, and cycling performance of these coatings in full Li‐ion cells.

Nondispersive Ultraviolet Visible Gas Analyzer for Monitoring Molybdenum Chloride and Oxychloride Precursors During Vapor Deposition Processes.

Nondispersive ultraviolet visible gas analyzer designs were evaluated for monitoring molybdenum-containing chloride and oxychloride precursor delivery during microelectronics vapor deposition processes. The performances of three analyzer designs, which differed only in the bandpass filter employed for wavelength selection, were compared for measuring the partial pressure of molybdenum pentachloride, molybdenum oxytetrachloride (MoOCl4), and molybdenum dioxydichloride (MoO2Cl2). The analyzer's optical response with a 369 nm center wavelength filter for molybdenum pentachloride was determined by measuring the molybdenum pentachloride absorbance as a function of vapor molar density. The calibrated analyzer was transferred to a process line on a deposition chamber and used to measure the molybdenum pentachloride partial pressure during delivery in a flowing carrier gas. The molybdenum pentachloride minimum detectable density was determined to be 1 × 10-4 mol m-3 (0.35 Pa for a cell temperature of 145 °C), for data collected at 1 kHz and referenced to a 0.2 s duration background. The analyzer optical response for molybdenum pentachloride with the two other filters and the response for MoOCl4 and MoO2Cl2 with all three filters were simulated with a simple model. These data were used to evaluate the sensitivity and selectivity of analyzers incorporating the different filters to some likely combinations of analytes and interferents.

Oxidative Molecular Layer Deposition of Conductive PEDOT Coatings Onto Polymer Sponges to Form Compressible Porous Electrodes

The formation of compressible porous sponge electrodes is appealing to overcome liquid phase diffusion in electrochemical applications including energy storage, water desalination, and electrocatalysis. Previous work has employed wet chemical synthesis to deliver conductive materials into porous polymer sponge supports, but these approaches struggle to produce functional electrodes due to (1) poor electrical connectivity of the conductive network and (2) mechanical rigidity of the foam after coating. In this work we employ oxidative molecular layer deposition (oMLD) via sequential gas-phase exposures of 3,4 ethylenedioxythiophene (EDOT) and molybdenum pentachloride (MoCl5) oxidant to coat polyurethane sponges with electrically-conductive and redox-active poly(3,4 ethylenedioxythiophene) (PEDOT) coatings. We analyze the oMLD deposition on compressible polyurethane sponges and modify the reaction conditions to obtain mechanically compressible and electrically conductive sponges. We specifically identify the importance MoCl5 dose time to enhance the conductivity of the sponges and the importance of EDOT purge time to preserve the mechanical properties of the sponges. This approach produces an electrically conductive PEDOT network within the sponge support with minimal impact on the sponge’s mechanical properties, offering advantages over wet-chemical synthesis approaches. The compressible, conductive sponges we generate have the potential to be used as compressible electrodes for water desalination, energy storage, and electrocatalysis.

Compressible sponge electrodes by oxidative molecular layer deposition (oMLD) of polyethylenedioxythiophene (PEDOT) onto open-cell polyurethane sponges

The formation of compressible porous sponge electrodes is appealing to overcome diffusion limitations in porous electrodes for applications including electrochemical energy storage, electrochemical water desalination, and electrocatalysis. Previous work has employed wet chemical synthesis to deliver conductive materials into porous polymer sponge supports, but these approaches struggle to produce functional electrodes due to (1) poor electrical connectivity of the conductive network and (2) mechanical rigidity of the foam after coating. In this work we employ oxidative molecular layer deposition (oMLD) via sequential gas-phase exposures of 3,4 ethylenedioxythiophene (EDOT) and molybdenum pentachloride (MoCl5) oxidant to imbibe polyurethane (PU) sponges with electrically-conductive and redox-active poly(3,4 ethylenedioxythiophene) (PEDOT) coatings. We analyze the oMLD deposition on compressive PU sponges and modify the reaction conditions to obtain mechanically compressible and electrically conductive sponge electrodes. We specifically identify the importance MoCl5 dose time to enhance the conductivity of the sponges and the importance of EDOT purge time to preserve the mechanical properties of the sponges. Controlling these variables produces an electrically conductive PEDOT network within the sponge support with reduced impact on the sponge’s mechanical properties, offering advantages over wet-chemical synthesis approaches. The compressible, conductive sponges we generate have the potential to be used as compressible electrodes for water desalination, energy storage, and electrocatalysis.

Low-resistivity molybdenum obtained by atomic layer deposition

A novel atomic layer deposition (ALD) process was developed for low-resistivity molybdenum (Mo) from molybdenum dichloride dioxide (MoCl2O2) and atomic hydrogen (at-H). A wide ALD window of self-limiting growth was observed between 150 and 450 °C. No film deposition occurred with molecular hydrogen (H2), demonstrating the necessity to have at-H to efficiently reduce the MoCl2O2 precursor. At 350 °C and above, the film composition was determined at approximately 95 at. % of Mo and 3.5 at % of oxygen (O), with trace amounts (i.e., <1 at. %) of carbon (C), chlorine (Cl), hydrogen (H), and nitrogen (N). The growth per cycle (GPC) was roughly 0.022 nm/cycle. No substrate selectivity or pronounced nucleation delay was observed on silicon (Si), silicon dioxide (SiO2), silicon nitride (Si3N4), silicon carbide (SiC), aluminum oxide (Al2O3), hafnium dioxide (HfO2), and low-k dielectric (SiOC). Film uniformity and conformality were ±5% and ±10%, respectively, while resistivity approached a bulk value of 18.6 μ Ω cm at 24 nm. At 250 °C and below, increased levels of oxygen (up to 33 at. % at 150 °C) and chlorine (2.7 at. % at 150 °C) were detected in the film. This trend coincided with an increase in the GPC, a change in optical properties, a decrease in film density and crystallinity, and an increase in resistivity. While self-limiting growth was observed through the entire ALD window of 150–450 °C, the temperature (T) range for depositing low-resistivity Mo deposition was narrower at T ≥ 250 °C.

Preparation and properties of high vinyl polybutadiene/sepiolite nanocomposites using a sepiolite immobilized Mo‐based catalyst

AbstractThe preparation of polymer/nanoclay nanocomposite has received much attention in recent years from both academic researchers and industry. The addition of nanoclay in polymer matrix could prepare material with improved performance and reduced cost. However, nanocaly is easy to agglomerate resulting in poor dispersion in the matrix. In this work, we proposed the immobilized catalyst prepared by coordination between molybdenum pentachloride (MoCl5) and hydroxyl groups on the nano sepiolite. The obtained sepiolite immobilized catalyst was used for the in situ polymerization of butadiene. The butadiene monomers were diffused into the tiny holes and channels of the sepiolite and sepiolite dispersed uniformly by the effect of in situ polymerization. The immobilization of sepiolite improves the dispersity of MoCl5 during polymerization and further enhances the activity of the catalyst. The coordination between sepiolite and MoCl5 results in a slight drop in vinyl content, and the molecular weight distribution remain unchanged. The flame retardant property of the nanocomposite was further investigated, and the result shows that the addition of sepiolite could increase the Oxygen index. This novel composite with well‐dispersed sepiolite and high content of vinyl can be further applied to flame‐retardant elastic materials.

Scalable growth of atomically thin MoS2 layers in a conventional MOCVD system using molybdenum dichloride dioxide as the molybdenum source

To bring atomically thin transition metal dichalcogenides (TMDs) to practical application, a highly reproducible process to grow them over a large scale is indispensable. Here, we develop a carbon-free reproducible route for the scalable growth of high-quality monolayer MoS2 by selecting molybdenum dichloride dioxide (MoO2Cl2) as the Mo source and integrating the precursor with a standard low-pressure cold-wall metalorganic chemical vapor deposition (MOCVD) system. Specifically, combined with H2S as the sulfur source and using catalytic Dragontrail glass (DT-glass) as the main substrate, we investigate the effect of MoO2Cl2 flux, temperature, and deposition time on the growth, confirming MoO2Cl2 with reasonably high vapor pressure is well compatible with the MOCVD system that enables precise control of sources for uniform nucleation and growth of MoS2 over a large area. We successfully demonstrate the growth of carbon-free MoS2 monolayers on DT-glass with decent crystalline, optical, and electrical properties. Additionally, the initial attempts also manifest that the proposed strategy could be generalized for growing ultrathin MoS2 on other technologically important substrates, such as SiO2/Si and quartz, exhibiting superior optical quality and wafer-scale uniformity. This work provides a new avenue for the large-scale production of high-quality MoS2 monolayers and facilitates their use in practical applications.

Expanding the Utility of β-Diketiminate Ligands in Heavy Group VI Chemistry of Molybdenum and Tungsten.

We report the synthesis of 17 molybdenum and tungsten complexes supported by the ubiquitous BDI ligand framework (BDI = β-diketiminate). The focal entry point is the synthesis of four molybdenum and tungsten(V) BDI complexes of the general formula [MO(BDIR)Cl2] [M = Mo, R = Dipp (1); M = W, R = Dipp (2); M = Mo, R = Mes (3); M = W, R = Mes (4)] synthesized by the reaction between MoOCl3(THF)2 or WOCl3(THF)2 and LiBDIR. Reactivity studies show that the BDIDipp complexes are excellent precursors toward adduct formation, reacting smoothly with dimethylaminopyridine (DMAP) and triethylphosphine oxide (OPEt3). No reaction with small phosphines has been observed, strongly contrasting the chemistry of previously reported rhenium(V) complexes. Additionally, the complexes 1 and 2 are good precursors for salt metathesis reactions. While 1 can be chemically reduced to the first stable example of a Mo(IV) BDI complex 15, reduction of 2 resulted in degradation of the BDI ligand via a nitrene transfer reaction, leading to MAD (4-((2,6-diisopropylphenyl)imino)pent-2-enide) supported tungsten(V) and tungsten(VI) complexes 16 and 17. All reported complexes have been thoroughly studied by VT-NMR and (heteronuclear) NMR spectroscopy, as well as UV-vis and EPR spectroscopy, IR spectroscopy, and X-ray diffraction analysis.

Greatly increased electrical conductivity of PBTTT-C14 thin film via controllable single precursor vapor phase infiltration

Doping is an important strategy for effectively regulating the charge carrier concentration of semiconducting materials. In this study, the electronic properties of organic–inorganic hybrid semiconducting polymers, synthesized via in situ controlled vapor phase infiltration (VPI) of poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-C14) with the metal precursors molybdenum pentachloride (MoCl5) and titanium tetrachloride (TiCl4), were altered and characterized. The conductivities of the infiltration-doped PBTTT-C14 thin films were enhanced by up to 9 and 4 orders of magnitude, respectively. The significantly improved electrical properties may result from interactions between metal atoms in the metal precursors and sulfur of the thiophene rings, thus forming new chemical bonds. Importantly, VPI doping has little influence on the structure of the PBTTT-C14 thin films. Even if various dopant molecules infiltrate the polymer matrix, the interlayer spacing of the films will inevitably expand, but it has negligible effects on the overall morphology and structure of the film. Also, Lewis acid-doped PBTTT-C14 thin films exhibited excellent environmental stability. Therefore, the VPI-based doping process has great potential for use in processing high-quality conductive polymer films.

Origin of Decomposition in a Family of Molybdenum Precursor Compounds.

The bis(tert-butylimido)-molybdenum(VI) framework has been used successfully in the design of vapor-phase precursors for molybdenum-containing thin films, so understanding its thermal behavior is important for such applications. Here, we report the thermal decomposition mechanism for a series of volatile bis(alkylimido)-dichloromolybdenum(VI) adducts with neutral N,N'-chelating ligands, to probe the stability and decomposition pathways for these molecules. The alkyl groups explored were tert-butyl, tert-pentyl, 1-adamantyl, and a cyclic imido (from 2,5-dimethylhexane-2,5-diamine). We also report the synthesis of the new tert-octyl imido adducts, (tOctN)2MoCl2·L (L = N,N,N',N'-tetramethylethylenediamine or 2,2'-bipyridine), which have been fully characterized by spectroscopic techniques as well as single-crystal X-ray diffraction and thermal analysis. We found that the decomposition of all compounds follows the same general pathway, proceeding first by the dissociation of the chelating ligand to give the coordinatively unsaturated species (RN)2MoCl2. Subsequent dimerization results in either an imido bridged adduct, [(RN)Mo(μ-NR)Cl2]2, or a chloride bridged adduct, [(RN)2Mo(μ-Cl)Cl]2, depending on the size of the R group. The dimeric species then likely undergoes an intramolecular γ-hydrogen transfer to yield a nitrido-amido adduct, (RHN)MoNCl2, and an alkene. Ultimately, the resulting molybdenum species appears to decompose into free tert-alkylamine and Mo2N or Mo2C. The thermolysis reactions have been monitored using 1H NMR spectroscopy, and the volatile decomposition products were analyzed using gas chromatography-mass spectrometry. A key intermediate has also been detected using electron ionization high-resolution mass spectrometry. Finally, a detailed computational investigation supports the mechanism outlined above and helps explain the relative stabilities of different N,N'-chelated bis(alkylimido)-dichloromolybdenum(VI) adducts.

Pentamethylcyclopentadienyl Molybdenum(V) Complexes Derived from Iodoanilines: Synthesis, Structure, and ROP of ε-Caprolactone

The reaction of [Mo(η-C5Me5)Cl4] with the ortho-, meta-, or para-iodo-functionalized anilines 2-IC6H4NH2, 3-IC6H4NH2, 4-IC6H4NH2 yields imido or amine products of the type [Mo(η-C5Me5)Cl2(IC6H4N)] (2-I, 1, 3-I, 3, 4-I, 5) or [Mo(η-C5Me5)Cl4(IC6H4NH2)] (3-I, 2, 4-I, 4), respectively, depending on the reaction stoichiometry/conditions; we were unable to isolate an amine complex of the 2-I derivative. The reaction of [Mo(η-C5Me5)Cl4] with one equivalent of 2-I,4-FC6H3NH2 in the presence of Et3N afforded [Mo(η-C5Me5)Cl2(2-I,4-FC6H3N)]·MeCN (6·MeCN), which, upon exposure to air, afforded the Mo(VI) imido complex [Mo(η-C5Me5)Cl3(2-I,4-FC6H3N)] (7). For comparative studies, the structure of the aniline (C6H5NH2)-derived complex [Mo(η-C5Me5)Cl2(2-C6H3N)] (8) has also been prepared. The molecular structures of 1–8 have been determined and reveal packing in the form of zig-zag chains or ladders. The complexes catalyze, in the presence of benzyl alcohol under N2, the ring-opening polymerization (ROP) of ε-caprolactone affording relatively low molecular weight products. The MALDI-ToF spectra indicate that a number of polymer series bearing a variety of end groups are formed. Conducting the ROPs as melts or under air results in the isolation of higher molecular weight products, again bearing a variety of end groups. Kinetic studies reveal the aniline-derived imido complex 8 performs best, whilst a meta-iodo substituent and a Mo(V) centre are also found to be beneficial. The structures of the side products 2-IC6H4NH3Cl and 3-IC6H4NH3Cl are also reported.

Optimization of MoCl5 intercalation for low-resistance and low-damage exfoliated highly-oriented pyrolytic graphite

This study developed a damageless molybdenum pentachloride (MoCl5) intercalation doping process of exfoliated highly-oriented pyrolytic graphite (e-HOPG). We optimized the chemical concentration and reaction temperature and time for doping crystalline multilayer graphene. We found that thick e-HOPG films are more susceptible to intercalation damage than previously reported few-layer graphene. Lowering the chemical concentration reduced the damage; however, there was a trade-off between doping efficiency and damage. Efficient doping with a 77% reduction of sheet resistance without significant damage was achieved by further optimizing the reaction temperature and time with reduced chemical concentration. The correlation plots of G and 2D peak positions in the Raman spectra were used to analyze the strain and carrier density induced during the intercalation process and investigate the cause of damage. The stability of the intercalated e-HOPG was confirmed for storage in a nitrogen box for 40 weeks.

Investigating the active sites in molybdenum anchored nitrogen-doped carbon for alkaline oxygen evolution reaction

Developing durable and efficient non-precious-metal based catalysts for oxygen evolution reaction (OER) is highly desirable in the field of electrocatalysis. In this work, a series of novel Mo anchored N-doped carbon catalysts (denoted as Mo/NC-T) were prepared starting from the zeolitic imidazolate framework 8 (ZIF-8) precursor. Firstly, Mo doped ZIF-8 precursor (Mo/ZIF-8) with a regular polyhedron structure was formed through a simple ion-exchange method process between molybdenum pentachloride (MoCl5) and ZIF-8. Afterward, Mo/ZIF-8 was converted to Mo/NC-T through a two-step calcination process in nitrogen (N2) and ammonia (NH3). The as-synthesized Mo/NC-T samples exhibited superior electrocatalytic OER properties. The optimal sample at 650 °C (Mo/NC-650) presented a low overpotential of 320 mV at 10 mA cm−2, a Tafel slope of 71 mV dec-1, and an outstanding long-term stability for 30 h in 1 M KOH solution. The remarkable OER activity of Mo/NC-T could be ascribed to the structural stability of carbon matrix and the synergistic effect between Mo3+ (derived from Mo-C bonds) and pyridinic N. This work provides a novel perspective on the roles of Mo species in the N-doped carbon electrocatalysts for OER.

Nonthermal Plasma-Enhanced Chemical Vapor Deposition of Two-Dimensional Molybdenum Disulfide.

Molybdenum disulfide (MoS2) is being studied for a wide range of applications including lithium-ion batteries and hydrogen evolution reaction catalysts. In this paper, we present a single-step nonthermal plasma-enhanced chemical vapor deposition (PECVD) process for the production of two-dimensional MoS2. This method provides an alternative route to established CVD and plasma synthesis routes. The approach presented here synthesizes films in only a few minutes using elemental sulfur (S8) and molybdenum pentachloride (MoCl5) as precursors. Deposition utilizes a nonthermal inductively coupled plasma reactor and temperatures around 500 °C. Film growth characteristics and nucleation are studied as a function of precursor concentrations, argon flow rate, plasma power, and deposition time. Few-layer two-dimensional (MoS2) films were formed at low precursor concentrations. Films with nanoparticle-like features were formed when the precursor concentration was high. Noncontinuous nonstoichiometric films were found at low plasma power, while high plasma power led to continuous films with good stoichiometry. The vacancies and defects in these films may provide active sites for hydrogen evolution.

Imido silyl complexes of molybdenum: synthesis, structure, and unusual H2/silane exchange

Reaction of complex (ArN)Mo(H)(Cl)(PMe3)3 (1) with BPh3 and silane H3SiPh affords a new silyl complex (ArN)Mo(SiH2Ph)(Cl)(PMe3)2 (3) that catalyses facile H–H/Si–H exchange. EXSY experiments suggest that this exchange does not involve the classical pathways such as oxidative addition of hydrogen or silane to the complex or σ-bond metathesis. It is suggested that the exchange may occur in an FLP cage comprised by the complex and the silane.

Molybdenum(VI) oxide: New methods of synthesis and properties

Objectives. The present study aims to develop new methods for the synthesis of molybdenum(VI) oxide, which is a precursor for the synthesis of functional materials, as well as to investigate the physicochemical properties of the resulting oxide phases. Methods. The synthesized phases and the products of their thermolysis were studied by differential thermal analysis, IR spectroscopy, X-ray diffraction analysis, and granulometry. Results. Three methods for the synthesis of molybdenum(VI) oxide were developed, and the physicochemical properties of the oxide phases obtained were studied. The first method consisted in the reaction of molybdenum pentachloride with a 6.0–9.5 mol/L ammonia solution, the second one was the reaction of niobium pentachloride with a sulfuric acid solution, and the third method involved the reaction of ammonium molybdate with nitric acid, affording brown molybdenum(V) MoO(OH)3 hydroxide, a bright blue precipitate of molybdenum blue MoO2.75, and white hydrated oxide MoO3·H2O, respectively. Conclusions. A series of thermal and X-ray diffraction analysis demonstrated that in all cases the samples were amorphous phases. Heat treatment at 580 °C of the synthesized phases led to the formation of a rhombic modification of molybdenum trioxide. The lattice parameters and X-ray density were calculated for all thermolysis products. The effect of heat treatment on the particle size of the synthesized samples and their thermolysis products was studied. Particle size analysis demonstrated that particles of different diameters were formed depending on the synthetic method. The smallest particle size (0.3–0.6 µm) was found in molybdenum trioxide, a product of the thermolysis of the sample obtained by the reaction of molybdenum pentachloride with a concentrated ammonium solution.

Atomic layer deposited 2D MoS2 atomic crystals: from material to circuit

Atomic layer deposition (ALD) can be used for wafer-scale synthesis of 2D materials. In this paper, a novel, reliable, secure, low-cost, and high-efficiency process for the fabrication of MoS2 is introduced and investigated. The resulting 2D materials show high carrier-mobility as well as excellent electrical uniformity. Using molybdenum pentachloride (MoCl5) and hexamethyldisilathiane (HMDST) as ALD precursors, thickness-controlled MoS2 films are uniformly deposited on a 50 mm sapphire and a 100 mm silica substrate. This is done with a high growth-rate (up to 0.90 A/cycle). Large-scale top-gated FET arrays are fabricated using the films, with a room-temperature mobility of 0.56 cm2/(V·s) and a high on/off current ratio of 106. Excellent electrical uniformity is observed in the whole sapphire wafer. Additionally, logical circuits, including inverters, NAND, AND, NOR, and OR gates, are realized successfully with a high-k HfO2 dielectric layer. Our inverters exhibit a fast response frequency of 50 Hz and a DC-voltage gain of 4 at VDD = 4 V. These results indicate that the new method has the potential to synthesize high quality MoS2 films on a large-scale, with hypo-toxicity and enhanced efficiency, which can facilitate a broader range of applications in the future.

Preparation of high 1,2‐orientation butadiene‐styrene copolymer by coordination copolymerization with molybdenum‐based catalytic system

ABSTRACTIn this study, with Mo‐based catalytic systems consisting of molybdenum pentachloride (MoCl5) as the main catalyst, alkyl aluminum as the cocatalyst and organophosphorus compound as the ligand, high 1,2‐orientation butadiene (Bd)‐styrene (St) copolymers were prepared by the coordination polymerization. The effects of phosphorous ligand, alkyl aluminum, polymerization temperature, polymerization time and monomers feed ratios on the monomer conversion and intrinsic viscosity of copolymers were explored in detail. The experimental results indicated that with MoCl5•TBP (tributyl phosphate)/Al(OPhCH3)(i‐Bu)2 as the catalytic system to initiate Bd‐St copolymerization, the reactivity ratios of butadiene and styrene monomers are 3.64 and 0.16, and the 1,2‐structural content in the resulting copolymers is over 80%, regarded as high 1,2‐orientation Bd‐St copolymers. All these results provided a basis for the design of catalyst used to prepare high 1,2‐orientation Bd‐St rubber. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48897.

Towards high-volumetric performance of Na/Li-ion batteries: a better anode material with molybdenum pentachloride–graphite intercalation compounds (MoCl5–GICs)

MoCl5–GICs are demonstrated as advanced anodes for simultaneously achieving high volumetric capacity and long cycle life in Na-ion and Li-ion batteries, owing to a strong charge transfer chemical doping effect and strong interaction force between MoCl5 and graphite layers.

Synthesis and Characterization of Strongly Solvatochromic Molybdenum(III) Complexes.

A series of seven molybdenum(III) complexes with the general formula of [Mo(diimine)Cl4]- were synthesized and characterized by X-ray diffraction, IR, cyclic voltammetry (CV), and UV-vis. The complexes were discovered to be highly solvatochromic, showing shifts in λmax between ∼120 and 170 nm in solvents ranging from water to acetone. Varying the substituents on the diimine ligand influenced the absorption energy such that electron-withdrawing groups induced a red shift while electron-donating groups exhibited the opposite effect. The complexes were surprisingly stable in both acidic and basic solutions, and in the case where carboxylic acid substituents were present, additional shifts in the absorption maxima were observed, corresponding to the state of protonation of these groups. Both the MoIV/III and MoIII/II redox couples were observed in CV experiments and were complemented with density functional theory (DFT) calculations.