Tunable High Entropy Lanthanide Oxide Microspheres via Confined Electroprecipitation in Emulsion Droplet Scaffolds.

Emergent high entropy nanomaterials and their associated complex surface structure hold promise to unlock unique catalytic intermediate pathways and photonic/plasmonic interactions; however, synthetic strategies to tune the size, morphological, and stoichiometric properties remain limited. This work demonstrates a confined electro-precipitation mechanism for the formation of tunable, high-entropy oxide microspheres within emulsion droplet scaffolds. This mechanism complements a traditional confined electrodeposition mechanism and explains the previously observed anomalous formation of thermodynamically unfavorable particles, including lanthanide species. Mass transfer studies reveal that microsphere coverage over a surface may be tuned and modeled by using a time-dependent modified Levich equation. Additionally, morphological tuning was demonstrated as a function of experimental conditions, such as rotation rate and precursor concentration. Finally, extension to multimetallic species permitted the generation of high-entropy lanthanide oxide microspheres, which were confirmed to have equimolar stoichiometries via energy dispersive spectroscopy and inductively coupled plasma mass spectrometry. This novel method promises to generate tunable, complex oxides with applications to thermal catalysis, optics, and applications yet unknown.

Rational Design of a Cu Chelator That Mitigates Cu-Induced ROS Production by Amyloid Beta.

Alzheimer's disease severely perturbs transition metal homeostasis in the brain leading to the accumulation of excess metals in extracellular and intraneuronal locations. The amyloid beta protein binds these transition metals, ultimately causing severe oxidative stress in the brain. Metal chelation therapy is an approach to sequester metals from amyloid beta and relieve the oxidative stress. Here we have designed a mixed N/O donor Cu chelator inspired by the proposed ligand set of Cu in amyloid beta. We demonstrate that the chelator effectively removes Cu from amyloid beta and suppresses reactive oxygen species (ROS) production by redox silencing and radical scavenging both in vitro and in cellulo. The impact of ROS on the extent of oxidation of the different aggregated forms of the peptide is studied by mass spectrometry, which, along with other ROS assays, shows that the oligomers are pro-oxidants in nature. The aliphatic Leu34, which was previously unobserved, has been identified as a new oxidation site.

Iron Redox Shuttles with Wide Optical Gap Dyes for High-Voltage Dye-Sensitized Solar Cells.

A series of iron polypyridyl redox shuttles were synthesized in the 2+ and 3+ oxidation states and paired with a series of wide optical gap organic dyes with weak aryl ether electron-donating groups. High voltage dye-sensitized solar cell (HV-DSC) devices were obtained through controlling the redox shuttle energetics and dye donor structure. The use of aryl ether donor groups, in place of commonly used aryl amines, allowed for the lowering of the dye ground-state oxidation potential which enabled challenging to oxidize redox shuttles based on Fe2+ polypyridyl structures to be used in functional devices. By carefully designing a dye series that varies the number of alkyl chains for TiO2 surface protection, the recombination of electrons in TiO2 to the oxidized redox shuttle could be controlled, leading to HV-DSC devices of up to 1.4 V.

Synthesis, characterization, and electrocatalytic activity of bis(pyridylimino)isoindoline Cu(II) and Ni(II) complexes.

Two NNN pincer complexes of Cu(ii) and Ni(ii) with BPIMe- [BPIMe- = 1,3-bis((6-methylpyridin-2-yl)imino)isoindolin-2-ide] have been prepared and characterized structurally, spectroscopically, and electrochemically. The single crystal structures of the two complexes confirmed their distorted trigonal bipyramidal geometry attained by three equatorial N-atoms from the ligand and two axially positioned water molecules to give [Cu(BPIMe)(H2O)2]ClO4 and [Ni(BPIMe)(H2O)2]ClO4. Electrochemical studies of Cu(ii) and Ni(ii) complexes have been performed in acetonitrile to identify metal-based and ligand-based redox activity. When subjected to a saturated CO2 atmosphere, both complexes displayed catalytic activity for the reduction of CO2 with the Cu(ii) complex displaying higher activity than the Ni(ii) analogue. However, both complexes were shown to decompose into catalytically active heterogeneous materials on the electrode surface over extended reductive electrolysis periods. Surface analysis of these materials using energy dispersive spectroscopy as well as their physical appearance suggests the reductive deposition of copper and nickel metal on the electrode surface. Electrocatalysis and decomposition are proposed to be triggered by ligand reduction, where complex stability is believed to be tied to fluxional ligand coordination in the reduced state.

Electro- and Photochemical Reduction of CO2 by Molecular Manganese Catalysts: Exploring the Positional Effect of Second-Sphere Hydrogen-Bond Donors.

A series of molecular Mn catalysts featuring aniline groups in the second-coordination sphere has been developed for electrochemical and photochemical CO2 reduction. The arylamine moieties were installed at the 6 position of 2,2'-bipyridine (bpy) to generate a family of isomers in which the primary amine is located at the ortho- (1-Mn), meta- (2-Mn), or para-site (3-Mn) of the aniline ring. The proximity of the second-sphere functionality to the active site is a critical factor in determining catalytic performance. Catalyst 1-Mn, possessing the shortest distance between the amine and the active site, significantly outperformed the rest of the series and exhibited a 9-fold improvement in turnover frequency relative to parent catalyst Mn(bpy)(CO)3 Br (901 vs. 102 s-1 , respectively) at 150 mV lower overpotential. The electrocatalysts operated with high faradaic efficiencies (≥70 %) for CO evolution using trifluoroethanol as a proton source. Notably, under photocatalytic conditions, a concentration-dependent shift in product selectivity from CO (at high [catalyst]) to HCO2 H (at low [catalyst]) was observed with turnover numbers up to 4760 for formic acid and high selectivities for reduced carbon products.

Ligand-Directed Approach to Activity-Based Sensing: Developing Palladacycle Fluorescent Probes That Enable Endogenous Carbon Monoxide Detection.

Carbon monoxide (CO) is an emerging gasotransmitter and reactive carbon species with broad anti-inflammatory, cytoprotective, and neurotransmitter functions along with therapeutic potential for the treatment of cardiovascular diseases. The study of CO chemistry in biology and medicine relative to other prominent gasotransmitters such as NO and H2S remains challenging, in large part due to limitations in available tools for the direct visualization of this transient and freely diffusing small molecule in complex living systems. Here we report a ligand-directed activity-based sensing (ABS) approach to CO detection through palladium-mediated carbonylation chemistry. Specifically, the design and synthesis of a series of ABS probes with systematic alterations in the palladium-ligand environment (e.g., sp3-S, sp3-N, sp2-N) establish structure-activity relationships for palladacycles to confer selective reactivity with CO under physiological conditions. These fundamental studies led to the development of an optimized probe, termed Carbon Monoxide Probe-3 Ester Pyridine (COP-3E-Py), which enables imaging of CO release in live cell and brain settings, including monitoring of endogenous CO production that triggers presynaptic dopamine release in fly brains. This work provides a unique tool for studying CO in living systems and establishes the utility of a synthetic methods approach to activity-based sensing using principles of organometallic chemistry.

Enhanced Electrochemical CO2 Reduction by a Series of Molecular Rhenium Catalysts Decorated with Second-Sphere Hydrogen-Bond Donors.

A series of rhenium(I) fac-tricarbonyl complexes containing pendent arylamine functionality in the second coordination sphere have been developed and studied as electrocatalysts for carbon dioxide (CO2) reduction. Aniline moieties were appended at the 6 position of a 2,2'-bipyridine (bpy) donor in which the primary amine was positioned at the ortho- (1-Re), meta- (2-Re), and para- (3-Re) sites of the aniline substituent to generate a family of isomers. The relationship between the catalyst structure and activity was explored across the series, and the catalytic performance was compared to that of the benchmark catalyst Re(bpy)(CO)3Cl (ReBpy). Catalysts 1-Re, 2-Re, and 3-Re outperform the benchmark catalyst both in anhydrous acetonitrile and with added trifluoroethanol (TFE) as an external proton source. In the presence of TFE, the aniline-substituted catalysts convert CO2 to carbon monoxide (CO) with high Faradaic efficiencies (≥89%) and have superior turnover frequencies (TOFs) relative to ReBpy (72.9 s-1), with 2-Re having the highest TOF of the series at 239 s-1, a value that is twice that of the next most active catalyst. TOFs of 123 and 109 s-1 were observed for the ortho- and para-substituted aniline complexes (1-Re and 3-Re), respectively. Indeed, catalytic activities vary widely across the series, showing a high sensitivity to the position of the amine functionality relative to the rhenium active site. IR and UV-vis spectroelectrochemical experiments were conducted on the aniline-substituted systems, revealing important differences between the catalysts and mechanistic insight.

Copper-based redox shuttles supported by preorganized tetradentate ligands for dye-sensitized solar cells.

Three copper redox shuttles ([Cu(1)]2+/1+, [Cu(2)]2+/1+, and [Cu(3)]2+/1+) featuring tetradentate ligands were synthesized and evaluated computationally, electrochemically, and in dye-sensitized solar cell (DSC) devices using a benchmark organic dye, Y123. Neutral polyaromatic ligands with limited flexibility were targeted as a strategy to improve solar-to-electrical energy conversion by reducing voltage losses associated with redox shuttle electron transfer events. Inner-sphere electron transfer reorganization energies (λ) were computed quantum chemically and compared to the commonly used [Co(bpy)3]3+/2+ redox shuttle which has a reported λ value of 0.61 eV. The geometrically constrained biphenyl-based Cu redox shuttles investigated here have lower reorganization energies (0.34-0.53 eV) and thus can potentially operate with lower driving forces for dye regeneration (ΔGreg) in DSC devices when compared to [Co(bpy)3]3+/2+-based devices. The rigid tetradentate ligand design promotes more efficient electron transfer reactions leading to an improved JSC (14.1 mA cm-2), higher stability due to the chelate effect, and a decrease in VlossOC for one of the copper redox shuttle-based devices.

Synthesis of a Redox-Active NNP-Type Pincer Ligand and Its Application to Electrocatalytic CO2 Reduction With First-Row Transition Metal Complexes.

We report the synthesis of a rigid phosphine-substituted, redox-active pincer ligand and its application to electrocatalytic CO2 reduction with first-row transition metal complexes. The tridentate ligand was prepared by Stille coupling of 2,8-dibromoquinoline and 2-(tributylstannyl)pyridine, followed by a palladium-catalyzed cross-coupling with HPPh2. Complexes were synthesized from a variety of metal precursors and characterized by NMR, high-resolution mass spectrometry, elemental analysis, and cyclic voltammetry. Formation of bis-chelated metal complexes, rather than mono-chelated complexes, was favored in all synthetic conditions explored. The complexes were assessed for their ability to mediate electrocatalytic CO2 reduction, where the cobalt complex was found to have the best activity for CO2-to-CO conversion in the presence of water as an added proton source.

Durable Solar-Powered Systems with Ni-Catalysts for Conversion of CO2 or CO to CH4.

Photocatalytic conversion of CO2 to reduced carbon states using sunlight and an earth-abundant catalyst could provide a critically needed source of renewable energy. Very few earth-abundant catalysts have shown CO2 to CH4 reactivity, and significant opportunities exist to improve catalyst durability. Through the strategic design of a novel, redox-active bipyridyl- N-heterocyclic carbene macrocyclic ligand complexed with nickel, CO2 is converted into the energy-rich solar fuel, CH4, photocatalytically with a photosensitizer in the presence of water. Up to 19 000 turnovers of CH4 from CO2 are observed. An exceptional turnover number of 570 000 for CH4 production via a photodriven formal hydrogenation of CO to CH4 was also found. This unique reactivity from a tunable, highly durable macrocyclic framework was studied via a series of photocatalytic and electrocatalytic reactions varying the atmospheric composition, as well as by isotopic labeling experiments and quantum yield calculations to evaluate the effect of ligand structure on product generation.

Photochemical CO2 reduction with mononuclear and dinuclear rhenium catalysts bearing a pendant anthracene chromophore.

A series of anthracene-substituted mononuclear and dinuclear rhenium complexes have been studied for photocatalytic CO2 reduction. The effects on catalytic activity of one versus two covalently-linked active sites, their relative proximity to one another, and the pendant organic chromophore are discussed.

Electrocatalytic CO2 Reduction with Cis and Trans Conformers of a Rigid Dinuclear Rhenium Complex: Comparing the Monometallic and Cooperative Bimetallic Pathways.

Anthracene-bridged dinuclear rhenium complexes are reported for electrocatalytic carbon dioxide (CO2) reduction to carbon monoxide (CO). Related by hindered rotation of each rhenium active site to either side of the anthracene bridge, cis and trans conformers have been isolated and characterized. Electrochemical studies reveal distinct mechanisms, whereby the cis conformer operates via cooperative bimetallic CO2 activation and conversion and the trans conformer reduces CO2 through well-established single-site and bimolecular pathways analogous to Re(bpy)(CO)3Cl. Higher turnover frequencies are observed for the cis conformer (35.3 s-1) relative to the trans conformer (22.9 s-1), with both outperforming Re(bpy)(CO)3Cl (11.1 s-1). Notably, at low applied potentials, the cis conformer does not catalyze the reductive disproportionation of CO2 to CO and CO32- in contrast to the trans conformer and mononuclear catalyst, demonstrating that the orientation of active sites and structure of the dinuclear cis complex dictate an alternative catalytic pathway. Further, UV-vis spectroelectrochemical experiments demonstrate that the anthracene bridge prevents intramolecular formation of a deactivated Re-Re-bonded dimer. Indeed, the cis conformer also avoids intermolecular Re-Re bond formation.

Electrocatalytic CO2 reduction with nickel complexes supported by tunable bipyridyl-N-heterocyclic carbene donors: understanding redox-active macrocycles.

A series of nickel complexes featuring redox-active macrocycles is reported for electrocatalytic CO2 reduction. A remarkable structure-activity relationship is elucidated from the series through electrochemical studies and DFT calculations, wherein a fine electronic balance between metal and ligand redox chemistry dictates selectivity for CO2 reduction versus the competing proton reduction reaction.

Electrocatalytic Reduction of CO2 to CO With Re-Pyridyl-NHCs: Proton Source Influence on Rates and Product Selectivities.

A series of four electron-deficient-substituted Re(I) pyridyl N-heterocyclic carbene (pyNHC) complexes have been synthesized, and their electrocatalytic reduction of CO2 has been evaluated by cyclic voltammetry and controlled potential electrolysis experiments. All of the catalysts were evaluated by cyclic voltammetry under inert atmosphere and under CO2 and compared to the known benchmark catalyst Re(bpy)(CO)3Br. Among the four Re-NHC catalysts, Re(pyNHC-PhCF3)(CO)3Br (2) demonstrated the highest catalytic rate (icat/ip)(2) at the first and second reduction events with a value of 4 at the second reduction potential (TOF = 0.8 s(-1)). The rate of catalysis was enhanced through the addition of proton sources (PhOH, TFE, and H2O; TOF up to 100 s(-1); (icat/ip)(2) = 700). Controlled potential electrolysis shows Faradaic efficiencies (FE) for CO production and accumulated charge for the Re(pyNHC-PhCF3)(CO)3Br catalyst exceed those of the benchmark catalyst in the presence of 2 M H2O (92%, 13 C at 1 h versus 61%, 3 C for the benchmark catalyst) under analogous experimental conditions. A peak FE of 100% was observed during electrolysis with Re(pyNHC-PhCF3)(CO)3Br.

Bioinspired design of redox-active ligands for multielectron catalysis: effects of positioning pyrazine reservoirs on cobalt for electro- and photocatalytic generation of hydrogen from water.

Mononuclear metalloenzymes in nature can function in cooperation with precisely positioned redox-active organic cofactors in order to carry out multielectron catalysis. Inspired by the finely tuned redox management of these bioinorganic systems, we present the design, synthesis, and experimental and theoretical characterization of a homologous series of cobalt complexes bearing redox-active pyrazines. These donor moieties are locked into key positions within a pentadentate ligand scaffold in order to evaluate the effects of positioning redox non-innocent ligands on hydrogen evolution catalysis. Both metal- and ligand-centered redox features are observed in organic as well as aqueous solutions over a range of pH values, and comparison with analogs bearing redox-inactive zinc(ii) allows for assignments of ligand-based redox events. Varying the geometric placement of redox non-innocent pyrazine donors on isostructural pentadentate ligand platforms results in marked effects on observed cobalt-catalyzed proton reduction activity. Electrocatalytic hydrogen evolution from weak acids in acetonitrile solution, under diffusion-limited conditions, reveals that the pyrazine donor of axial isomer 1-Co behaves as an unproductive electron sink, resulting in high overpotentials for proton reduction, whereas the equatorial pyrazine isomer complex 2-Co is significantly more active for hydrogen generation at lower voltages. Addition of a second equatorial pyrazine in complex 3-Co further minimizes overpotentials required for catalysis. The equatorial derivative 2-Co is also superior to its axial 1-Co congener for electrocatalytic and visible-light photocatalytic hydrogen generation in biologically relevant, neutral pH aqueous media. Density functional theory calculations (B3LYP-D2) indicate that the first reduction of catalyst isomers 1-Co, 2-Co, and 3-Co is largely metal-centered while the second reduction occurs at pyrazine. Taken together, the data establish that proper positioning of non-innocent pyrazine ligands on a single cobalt center is indeed critical for promoting efficient hydrogen catalysis in aqueous media, akin to optimally positioned redox-active cofactors in metalloenzymes. In a broader sense, these findings highlight the significance of electronic structure considerations in the design of effective electron-hole reservoirs for multielectron transformations.

Structure and electronic configurations of the intermediates of water oxidation in blue ruthenium dimer catalysis.

Catalytic O(2) evolution with cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+) (bpy is 2,2-bipyridine), the so-called blue dimer, the first designed water oxidation catalyst, was monitored by UV-vis, EPR, and X-ray absorption spectroscopy (XAS) with ms time resolution. Two processes were identified, one of which occurs on a time scale of 100 ms to a few seconds and results in oxidation of the catalyst with the formation of an intermediate, here termed [3,4]'. A slower process occurring on the time scale of minutes results in the decay of this intermediate and O(2) evolution. Spectroscopic data suggest that within the fast process there is a short-lived transient intermediate, which is a precursor of [3,4]'. When excess oxidant was used, a highly oxidized form of the blue dimer [4,5] was spectroscopically resolved within the time frame of the fast process. Its structure and electronic state were confirmed by EPR and XAS. As reported earlier, the [3,4]' intermediate likely results from reaction of [4,5] with water. While it is generated under strongly oxidizing conditions, it does not display oxidation of the Ru centers past [3,4] according to EPR and XAS. EXAFS analysis demonstrates a considerably modified ligand environment in [3,4]'. Raman measurements confirmed the presence of the O-O fragment by detecting a new vibration band in [3,4]' that undergoes a 46 cm(-1) shift to lower energy upon (16)O/(18)O exchange. Under the conditions of the experiment at pH 1, the [3,4]' intermediate is the catalytic steady state form of the blue dimer catalyst, suggesting that its oxidation is the rate-limiting step.

Electronic structure of the water oxidation catalyst cis,cis-[(bpy)2(H2O)Ru(III)ORu(III)(OH2)(bpy)2]4+, the blue dimer.

The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+). Although there is experimental evidence for extensive electronic coupling across the µ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru(III) ions across the µ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK(a) values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru(III) appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ(1)*)(2) with a low-lying, paramagnetic triplet state (dπ(1)*)(1)(dπ(2)*)(1). Systematic structural-magnetic-IR correlations are observed between ν(sym)(RuORu) and ν(asym)(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, µ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with ∠Ru-O-Ru dictated by the distortion and electron-electron repulsion.

Proton-coupled electron transfer at modified electrodes by multiple pathways.

In single site water or hydrocarbon oxidation catalysis with polypyridyl Ru complexes such as [Ru(II)(Mebimpy)(bpy)(H(2)O)](2+) [where bpy is 2,2'-bipyridine, and Mebimpy is 2,6-bis(1-methylbenzimidazol-2-yl)pyridine] 2, or its surface-bound analog [Ru(II)(Mebimpy)(4,4'-bis-methlylenephosphonato-2,2'-bipyridine)(OH(2))](2+) 2-PO(3)H(2), accessing the reactive states, Ru(V) = O(3+)/Ru(IV) = O(2+), at the electrode interface is typically rate limiting. The higher oxidation states are accessible by proton-coupled electron transfer oxidation of aqua precursors, but access at inert electrodes is kinetically inhibited. The inhibition arises from stepwise mechanisms which impose high energy barriers for 1e- intermediates. Oxidation of the Ru(III)-OH(2+) or forms of 2-PO(3)H(2) to Ru(IV) = O(2+) on planar fluoride-doped SnO(2) electrode and in nanostructured films of Sn(IV)-doped In(2)O(3) and TiO(2) has been investigated with a focus on identifying microscopic phenomena. The results provide direct evidence for important roles for the nature of the electrode, temperature, surface coverage, added buffer base, pH, solvent, and solvent H(2)O/D(2)O isotope effects. In the nonaqueous solvent, propylene carbonate, there is evidence for a role for surface-bound phosphonate groups as proton acceptors.

Understanding the electronic structure of 4d metal complexes: from molecular spinors to L-edge spectra of a di-Ru catalyst.

L(2,3)-edge X-ray absorption spectroscopy (XAS) has demonstrated unique capabilities for the analysis of the electronic structure of di-Ru complexes such as the blue dimer cis,cis-[Ru(III)(2)O(H(2)O)(2)(bpy)(4)](4+) water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH(3))(6)](3+) model complex show considerably different splitting of the Ru L(2,3) absorption edge, which reflects changes in the relative energies of the Ru 4d orbitals caused by hybridization with a bridging ligand and spin-orbit coupling effects. To aid the interpretation of spectroscopic data, we developed a new approach, which computes L(2,3)-edges XAS spectra as dipole transitions between molecular spinors of 4d transition metal complexes. This allows for careful inclusion of the spin-orbit coupling effects and the hybridization of the Ru 4d and ligand orbitals. The obtained theoretical Ru L(2,3)-edge spectra are in close agreement with experiment. Critically, existing single-electron methods (FEFF, FDMNES) broadly used to simulate XAS could not reproduce the experimental Ru L-edge spectra for the [Ru(NH(3))(6)](3+) model complex nor for the blue dimer, while charge transfer multiplet (CTM) calculations were not applicable due to the complexity and low symmetry of the blue dimer water oxidation catalyst. We demonstrated that L-edge spectroscopy is informative for analysis of bridging metal complexes. The developed computational approach enhances L-edge spectroscopy as a tool for analysis of the electronic structures of complexes, materials, catalysts, and reactive intermediates with 4d transition metals.

Surface activation of electrocatalysis at oxide electrodes. Concerted electron-proton transfer.

Dramatic rate enhancements are observed for the oxidation of phenols, including tyrosine, at indium-tin oxide electrodes modified by the addition of the electron-transfer relays [M(II)(bpy)(2)(4,4'-(HO)(2)P(O)CH(2))(2)bpy)](2+) (M = Ru, Os) with clear evidence for the importance of proton-coupled electron transfer and concerted electron-proton transfer.