Dmitry E. Polyansky
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View article: Correlated solvent coordinates accelerate multi-donor proton-coupled electron transfer
Correlated solvent coordinates accelerate multi-donor proton-coupled electron transfer Open
Multiple donors accelerate intramolecular PCET rates beyond statistical predictions. The partial sharing of solvent polarization between equivalent sites lowers the effective outer sphere reorganization energy.
View article: Tuning the Photocatalytic CO<sub>2</sub> Reduction through <i>para</i>-Substituents in Bipyridyl Rhenium Complexes
Tuning the Photocatalytic CO<sub>2</sub> Reduction through <i>para</i>-Substituents in Bipyridyl Rhenium Complexes Open
Six fac-[Re-(NN)-(CO)3Cl] complexes, where NN is a 2,2'-bipyridine ligand with systematically varied electron-donating or -withdrawing groups at the 4,4' positions, were explored as photocatalysts for CO2 reduction to CO. The light absorpt…
View article: Transient methods for understanding the properties of strongly oxidizing radicals
Transient methods for understanding the properties of strongly oxidizing radicals Open
The properties of strongly oxidizing radicals are probed by photochemical or radiolytic transient techniques.
View article: Controlling Product Selectivity in Photochemical CO<sub>2</sub> Reduction with the Redox Potential of the Photosensitizer
Controlling Product Selectivity in Photochemical CO<sub>2</sub> Reduction with the Redox Potential of the Photosensitizer Open
The ability to selectively reduce CO2 to a particular product or mixture of products is expected to play a key role in mitigation strategies aiming to alleviate the devastating impact of this greenhouse gas in our climate and oceans. Among…
View article: Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO<sub>2</sub>
Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO<sub>2</sub> Open
It is well-known that addition of a cationic functional group to a molecule lowers the necessary applied potential for an electron transfer (ET) event. This report studies the effect of a proton (a cation) on the mechanism of electrochemic…
View article: Reduction of CO to Methanol with Recyclable Organic Hydrides
Reduction of CO to Methanol with Recyclable Organic Hydrides Open
The reaction steps for the selective conversion of a transition metal carbonyl complex to a hydroxymethyl complex that releases methanol upon irradiation with visible light have been successfully quantified in acetonitrile solution with di…
View article: Combined Effects of Hemicolligation and Ion Pairing on Reduction Potentials of Biphenyl Radical Cations
Combined Effects of Hemicolligation and Ion Pairing on Reduction Potentials of Biphenyl Radical Cations Open
Formal reduction potentials of highly oxidizing and short-lived radical cations of substituted biphenyls generated by pulse radiolysis in 1,2-dichloroethane (DCE) were measured using a redox equilibrium ladder method. The effect of halide …
View article: CCDC 2252977: Experimental Crystal Structure Determination
CCDC 2252977: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: Lewis Acids and Electron-Withdrawing Ligands Accelerate CO Coordination to Dinuclear Cu<sup>I</sup> Compounds
Lewis Acids and Electron-Withdrawing Ligands Accelerate CO Coordination to Dinuclear Cu<sup>I</sup> Compounds Open
A series of dinuclear molecular copper complexes were prepared and used to model the binding and Lewis acid stabilization of CO in heterogeneous copper CO2 reduction electrocatalysts. Experimental studies (including measurement of rate and…
View article: Mechanistic roles of metal- and ligand-protonated species in hydrogen evolution with [Cp*Rh] complexes
Mechanistic roles of metal- and ligand-protonated species in hydrogen evolution with [Cp*Rh] complexes Open
Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides. However, some organometallic species supported by η 5 -pentamethylcyclopentadienyl (C…
View article: CCDC 2226377: Experimental Crystal Structure Determination
CCDC 2226377: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 2226376: Experimental Crystal Structure Determination
CCDC 2226376: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 2243811: Experimental Crystal Structure Determination
CCDC 2243811: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: Multi-Electron Transfer at H-Terminated p-Si Electrolyte Interfaces: Large Photovoltages under Inversion Conditions
Multi-Electron Transfer at H-Terminated p-Si Electrolyte Interfaces: Large Photovoltages under Inversion Conditions Open
Photovoltages for hydrogen-terminated p-Si(111) in an acetonitrile electrolyte were quantified with methyl viologen [1,1'-(CH3)2-4,4'-bipyridinium](PF6)2, abbreviated MV2+, and [Ru(bpy)3](PF6)2, where bpy is 2,2'-bipyridine, that respectiv…
View article: A Dicationic <i>fac</i>-Re(bpy)(CO)<sub>3</sub>Cl for CO<sub>2</sub> Electroreduction at a Reduced Overpotential
A Dicationic <i>fac</i>-Re(bpy)(CO)<sub>3</sub>Cl for CO<sub>2</sub> Electroreduction at a Reduced Overpotential Open
A dicationic Re bipyridine-type complex, fac-Re(6,6'-(2-((trimethylammonio)-methyl)phenyl)-2,2'-bipyridine )(CO)3Cl hexafluorophosphate (12+), has been synthesized, and its electrochemical behavior under Ar and CO2 has been investigated. T…
View article: <i>In Situ</i> Attenuated Total Reflectance Infrared Spectroelectrochemistry (ATR-IR-SEC) for the Characterization of Molecular Redox Processes on Surface-Proximal Doped Silicon ATR Crystal Working Electrodes
<i>In Situ</i> Attenuated Total Reflectance Infrared Spectroelectrochemistry (ATR-IR-SEC) for the Characterization of Molecular Redox Processes on Surface-Proximal Doped Silicon ATR Crystal Working Electrodes Open
In situ mid-infrared spectroscopy is a powerful technique for understanding the mechanism of CO2 reduction (CO2R) catalysts because it enables the direct detection of catalytic intermediates and products. Moreover, spectroelectrochemistry …
View article: Mechanistic Roles of Metal- and Ligand-Protonated Species in Hydrogen Evolution with [Cp*Rh] Complexes
Mechanistic Roles of Metal- and Ligand-Protonated Species in Hydrogen Evolution with [Cp*Rh] Complexes Open
Protonation reactions involving organometallic complexes are ubiquitous in redox chemistry and often result in the generation of reactive metal hydrides. However, some organometallic species supported by η5-pentamethylcyclopentadienyl (Cp*…
View article: Understanding the Role of Inter- and Intramolecular Promoters in Electro- and Photochemical CO<sub>2</sub> Reduction Using Mn, Re, and Ru Catalysts
Understanding the Role of Inter- and Intramolecular Promoters in Electro- and Photochemical CO<sub>2</sub> Reduction Using Mn, Re, and Ru Catalysts Open
Recycling of carbon dioxide to fuels and chemicals is a promising strategy for renewable energy storage. Carbon dioxide conversion can be achieved by (i) artificial photosynthesis using photoinduced electrons; (ii) electrolysis using elect…
View article: Role of Bimetallic Interactions in the Enhancement of Catalytic CO<sub>2</sub> Reduction by a Macrocyclic Cobalt Catalyst
Role of Bimetallic Interactions in the Enhancement of Catalytic CO<sub>2</sub> Reduction by a Macrocyclic Cobalt Catalyst Open
The use of two metal centers in a CO2 reduction catalyst that work together synergistically, with similar or complementary functions, can potentially lead to a significant reduction in overpotential, enhance catalytic activity and/or selec…
View article: CCDC 2049767: Experimental Crystal Structure Determination
CCDC 2049767: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 2049766: Experimental Crystal Structure Determination
CCDC 2049766: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: CCDC 2049765: Experimental Crystal Structure Determination
CCDC 2049765: Experimental Crystal Structure Determination Open
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available …
View article: Photochemical CO<sub>2</sub> Reduction Using Rhenium(I) Tricarbonyl Complexes with Bipyridyl‐Type Ligands with and without Second Coordination Sphere Effects
Photochemical CO<sub>2</sub> Reduction Using Rhenium(I) Tricarbonyl Complexes with Bipyridyl‐Type Ligands with and without Second Coordination Sphere Effects Open
The front cover artwork is provided by Elena Amadio, University of Torino (Italy). The image shows the photocatalytic reduction of CO 2 to CO by an aniline‐substituted Re‐bpy catalyst in the presence of a strong electron donor (BIH). Read …
View article: Front Cover: Photochemical CO<sub>2</sub> Reduction Using Rhenium(I) Tricarbonyl Complexes with Bipyridyl‐Type Ligands with and without Second Coordination Sphere Effects (ChemPhotoChem 6/2021)
Front Cover: Photochemical CO<sub>2</sub> Reduction Using Rhenium(I) Tricarbonyl Complexes with Bipyridyl‐Type Ligands with and without Second Coordination Sphere Effects (ChemPhotoChem 6/2021) Open
The Front Cover illustrates the photocatalytic reduction of CO2 to CO by an aniline-substituted Re-bipyridine-type photocatalyst in the presence of a strong electron donor (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]-imidazole=BIH) in N,…
View article: Structural and Electronic Influences on Rates of Tertpyridine−Amine Co<sup>III</sup>−H Formation During Catalytic H<sub>2</sub> Evolution in an Aqueous Environment
Structural and Electronic Influences on Rates of Tertpyridine−Amine Co<sup>III</sup>−H Formation During Catalytic H<sub>2</sub> Evolution in an Aqueous Environment Open
In this work, the differences in catalytic performance for a series of Co hydrogen evolution catalysts with different pentadentate polypyridyl ligands (L), have been rationalized by examining elementary steps of the catalytic cycle using a…
View article: Photochemical CO<sub>2</sub> Reduction Using Rhenium(I) Tricarbonyl Complexes with Bipyridyl‐Type Ligands with and without Second Coordination Sphere Effects
Photochemical CO<sub>2</sub> Reduction Using Rhenium(I) Tricarbonyl Complexes with Bipyridyl‐Type Ligands with and without Second Coordination Sphere Effects Open
The effect of phenyl, phenol, aniline, amino, and CF 3 substituents of the 2,2′‐bipyridine ligand in fac ‐ReCl(L)(CO) 3 (L=2,2′‐bipyridine derivative) catalysts on photochemical CO 2 reduction in dimethylacetamide is examined, in order to …
View article: Molecular Catalysts with Intramolecular Re–O Bond for Electrochemical Reduction of Carbon Dioxide
Molecular Catalysts with Intramolecular Re–O Bond for Electrochemical Reduction of Carbon Dioxide Open
A new Re bipyridine-type complex, namely, fac-Re(pmbpy)(CO)3Cl (pmbpy = 4-phenyl-6-(2-hydroxy-phenyl)-2,2'-bipyridine), 1, carrying a single OH moiety as local proton source, has been synthesized, and its electrochemical behavior under Ar …
View article: Comprehensive Mechanisms of Electrocatalytic CO<sub>2</sub> Reduction by [Ir(bip)(ppy)(CH<sub>3</sub>CN)](PF<sub>6</sub>)<sub>2</sub>
Comprehensive Mechanisms of Electrocatalytic CO<sub>2</sub> Reduction by [Ir(bip)(ppy)(CH<sub>3</sub>CN)](PF<sub>6</sub>)<sub>2</sub> Open
Examples of transition metal complexes capable of the dual roles of light harvesting and catalysis of CO2 reduction are rare. This self-sensitized approach simplifies systems and efficiencies; therefore complete understanding of mechanisti…