IR Spectroelectrochemistry Research Articles

Benzo[1,2-b:4,5-b’]dithiophene diethynyl bridged bimetallic ruthenium complexes: syntheses and characterization, (spectro)electrochemistry combined with theoretical calculations

We have constructed isomeric triruthenium ethynyl complexes 1 and 2 linked by benzo[1,2-b:4,5-b’]dithiophene. The electronic properties of 1 and 2 were compared by (spectro)electrochemical and theoretical calculations. DFT (density functional theory) fully-optimized structures 1 and 2 showed that the ruthenium terminal groups both exhibit a similar pseudo-octahedral configuration as reported for the crystal structure of 1. With step-by-step oxidation, the bond length of Ru-C decreases and the bond length of C≡C increases, which indicated that the complexes undergo a transition from Ru-C≡C to Ru = C = C. The electrochemical results of 1 and 2 featured two consecutive single-electron redox processes, and the ΔE value of 2 (329 mV) was significantly higher than that of 1 (140 mV). The near-IR broad absorptions of 2 + from UV-Vis-NIR spectroelectrochemistry exhibited a blue shift relative to that of 1 +, which could be attributed to MLCT (metal to ligand charge transfer) absorptions and confirmed by TDDFT (time dependent) calculations. The results suggested that the bridge ligands are involved in the redox process. The ν(C≡C) stretch of 2 + from IR spectroelectrochemistry exhibited a strong single peak at 1969 cm-1, while the isomer 1 + showed three asymmetric peaks. These results showed excellent charge delocalization ability of 2.

Diiron Complexes with Rigid and Conjugated S-to-S Bridges for Electrocatalytic Reduction of CO2.

Electroreduction of CO2 to value-added low-carbon chemicals is a promising way for carbon neutrality and CO2 utilization. It was found that the diiron complex [(μ-bdt)Fe2(CO)6] (bdt = benzene-1,2-dithiolate) has high catalytic activity for electrocatalytic CO2 reduction. To further study the effect of the S-to-S bridge on the catalytic performances of diiron complexes for electrochemical CO2 reduction, four diiron complexes 1-4 with different rigid and conjugated S-to-S bridges were either selected or designed. The electrocatalytic studies showed that under optimal conditions, 2 with a 2,3-naphthalenedithiolato bridge exhibited the lowest catalytic onset potential (Eonset = -1.75 V vs Fc+/0), while 4 with a diphenyl-1,2-vinylidene bridge displayed the highest catalytic activity (TOFmax = 295 s-1), which is 1.5 times that of [(μ-bdt)Fe2(CO)6]. The controlled potential electrolysis experiments of 4 in 0.1 M MeOH/MeCN at -2.35 V vs Fc+/0 gave a total faradaic yield close to 100%, with selectivities of 77%, 9%, and 14% for HCOOH, CO, and H2, respectively. The mechanism for CO2 reduction was studied using density functional theory, IR spectroelectrochemistry, and electrochemical methods. The results indicate that modifying the structure of the S-to-S bridge is an effective strategy to improve the catalytic performance of diiron complexes for electrocatalytic CO2 reduction.

3,6‐Divinyl‐N‐arylcarbazoles‐bridged diruthenium complexes bearing two Ru(CO)Cl(PiPr3)2 moieties: Polyelectrochromism and electronic coupling

A series of five 3,6‐divinyl‐N‐arylcarbazoles‐bridged diruthenium complexes with a general formula of [{Ru(CO)Cl(PiPr3)2}2(μ‐(CH=CH)2‐(N‐arylcarbazole)‐3,6); aryl = 4‐anisyl; [1a], 4‐tolyl; [1b], phenyl; [1c], 4‐(trifluoromethyl)phenyl; [1d], and 4‐nitrophenyl; [1e]] were successfully synthesized. These new square‐pyramidal bis(ruthenium‐vinyl)‐type complexes were characterized in their neutral state via classical NMR, UV/Vis, and IR spectroscopic techniques and in their three various accessible oxidized states via electrochemical techniques and ESR spectroscopy along with UV/Vis/NIR and IR spectroelectrochemistry as well as with DFT calculations. Our obtained results were compared with the closely related bis(ruthenium‐vinyl)‐appended N‐(4‐anisyl)diphenylamine TAARu2 counterpart of [1a]. Electrochemical studies on complexes [1a]–[1e] revealed three consecutive, chemically and electrochemically, well‐separated, reversible one‐electron oxidation processes at low and well‐accessible potentials. Their half‐wave potential separations ΔE½ between the individual redox waves and the derived comproportionation constants Kc1–Kc3 attribute to noteworthy stability of every oxidized intermediate state. The concert electrochemical and UV/Vis/NIR/IR spectro(electro)scopic results on these rotationally restricted N‐arylcarbazoles‐bridged bis(ruthenium‐alkenyl)‐type complexes [1a]–[1e] confirmed the relative weakness influence of altering the para‐substituent on the peripheral aryl ring. This is most probably due to the sizable torsion with nearly 55° between the co‐planarity of the carbazole heterocycle core and the peripheral N‐bound aryl ring. In their mixed‐valent (MV) radical states [1a]+–[1e]+, the observed pattern of two well‐separated Ru(C≡O) bands mirrors the uneven distribution of the uni‐positive charge over the two chemically equivalent bis(ruthenium‐vinyl) moieties as indicated by classical class II of Robin–Day classification of MV states.

An Electrocatalytic Cascade Reaction for the Synthesis of Ketones Using CO2 as a CO Surrogate

AbstractThe construction of carbonyl compounds via carbonylation reactions using safe CO sources remains a long‐standing challenge to synthetic chemists. Herein, we propose a catalyst cascade Scheme in which CO2 is used as a CO surrogate in the carbonylation of benzyl chlorides. Our approach is based on the cooperation between two coexisting catalytic cycles: the CO2‐to‐CO electroreduction cycle promoted by [Fe(TPP)Cl] (TPP=meso‐tetraphenylporphyrin) and an electrochemical carbonylation cycle catalyzed by [Ni(bpy)Br2] (2,2′‐bipyridine). As a proof of concept, this protocol allows for the synthesis of symmetric ketones from good to excellent yields in an undivided cell with non‐sacrificial electrodes. The reaction can be directly scaled up to gram‐scale and operates effectively at a CO2 concentration of 10 %, demonstrating its robustness. Our mechanistic studies based on cyclic voltammetry, IR spectroelectrochemistry and Density Functional Theory calculations suggest a synergistic effect between the two catalysts. The CO produced from CO2 reduction is key in the formation of the [Ni(bpy)(CO)2], which is proposed as the catalytic intermediate responsible for the C−C bond formation in the carbonylation steps.

An Electrocatalytic Cascade Reaction for the Synthesis of Ketones Using CO2 as a CO Surrogate.

The construction of carbonyl compounds via carbonylation reactions using safe CO sources remains a long-standing challenge to synthetic chemists. Herein, we propose a catalyst cascade Scheme in which CO2 is used as a CO surrogate in the carbonylation of benzyl chlorides. Our approach is based on the cooperation between two coexisting catalytic cycles: the CO2-to-CO electroreduction cycle promoted by [Fe(TPP)Cl] (TPP=meso-tetraphenylporphyrin) and an electrochemical carbonylation cycle catalyzed by [Ni(bpy)Br2] (2,2'-bipyridine). As a proof of concept, this protocol allows for the synthesis of symmetric ketones from good to excellent yields in an undivided cell with non-sacrificial electrodes. The reaction can be directly scaled up to gram-scale and operates effectively at a CO2 concentration of 10 %, demonstrating its robustness. Our mechanistic studies based on cyclic voltammetry, IR spectroelectrochemistry and Density Functional Theory calculations suggest a synergistic effect between the two catalysts. The CO produced from CO2 reduction is key in the formation of the [Ni(bpy)(CO)2], which is proposed as the catalytic intermediate responsible for the C-C bond formation in the carbonylation steps.

Structure Activity Relationships for Second‐Coordination Sphere Functional Group Dependent CO2 Reduction by Manganese Bipyridyl Electrocatalysts

AbstractA series of twelve second coordination sphere (SCS) functionalized manganese tricarbonyl bipyridyl complexes are investigated for their electrocatalytic CO2 reduction properties in acetonitrile. A qualitative and quantitative assessment of the SCS functional groups is discussed with respect to the catalysts’ thermodynamic and kinetic efficiencies, and their product selectivities. In probing a broad scope of functional groups, it is clear that only the aprotic ortho‐arylester SCS is capable of promoting the highly desired low‐overpotential proton‐transfer electron‐transfer (PT‐ET) pathway for selective CO production. The ortho‐phenolic analogues cause an increase in overpotential with a product selectivity favoring H2 evolution, consistent with a high‐overpotential pathway via the anionic [Mn−H]− intermediate. Alternative aprotic Lewis base functional groups such as trifluoromethyl, morpholine and acetamide are shown to also be capable of intermediate manganese hydride generation. The tertiary amine substituent, 2‐morpholinophenyl, exhibits a desirable product distribution characteristic of syn‐gas (CO : H2=30 : 48) with an impressive turnover frequency, while the secondary amine group, 2‐acetamidophenyl, induces a notable shift in selectivity with a faradaic yield of 55 % for the formate (HCO2−) product. In addition to their catalytic properties, cyclic voltammetry and infrared spectroelectrochemistry (IR‐SEC) studies are presented to probe pre‐catalyst electronic properties and the two‐electron reduction activation pathway.

Nitrile Substituents at the Conjugated Dipyridophenazine Moiety as Infrared Redox Markers in Electrochemically Reduced Heteroleptic Ru(II) Polypyridyl Complexes.

Ruthenium(II) complexes [Ru(tap)2(NN)]2+ (tap = 1,4,5,8-tetraazaphenanthrene, NN = 11-cyano-dipyrido[3,2-a:2',3'-c]phenazine (11-CN-dppz) and 11,12-dicyano-dipyrido[3,2-a:2',3'-c]phenazine (11,12-CN-dppz)) feature the C≡N groups as infrared (IR)-active redox markers. They were studied by cyclic voltammetry, UV-vis, and IR spectroelectrochemistry (SEC), and density functional theory calculations to assign the four 1e- reduction waves R1-R4 observed in dichloromethane. Generally, the NN ligands are reduced first (R1). For [Ru(tap)2(11,12-CN-dppz)]2+, R1 is sufficiently separated from R2 and delocalized over both tap ligands. Accordingly, IR SEC conducted at R1 shows a large red shift of the νs,as(C≡N) modes by -18/-28 cm-1, accompanied by a 4-fold enhancement of the νs(C≡N) intensity, comparably with reference data for free 11,12-CN-dppz. The first tap-based reduction of spin-doublet [Ru(tap)2(11,12-CN-dppz)]+ to spin-triplet [Ru(tap)2(11,12-CN-dppz)] at R2 decreased ν(C≡N) by merely -2 cm-1, while the intensity enhancement reached an overall factor of 8. Comparably, a red shift of ν(C≡N) by -27 cm-1 resulted from the 1e- reduction of [Ru(tap)2(11-CN-dppz)]2+ at R1 (poorly resolved from R2), and the intensity enhancement was roughly 3-fold. Concomitant 1e- reductions of the tap ligands (R2 and R3) caused only minor ν(C≡N) shifts of -3 cm-1 and increased the absorbance by overall factors of 6.5 and 8, respectively.

Ultrasensitive Plasmon-Enhanced Infrared Spectroelectrochemistry.

IR spectroelectrochemistry (EC-IR) is a cutting-edge operando method for exploring electrochemical reaction mechanisms. However, detection of interfacial molecules is challenged by the limited sensitivity of existing EC-IR platforms due to the lack of high-enhancement substrates. Here, we propose an innovative plasmon-enhanced infrared spectroelectrochemistry (EC-PEIRS) platform to overcome this sensitivity limitation. Plasmonic antennae with ultrahigh IR signal enhancement are electrically connected via monolayer graphene while preserving optical path integrity, serving as both the electrode and IR substrate. The [Fe(CN)6 ]3- /[Fe(CN)6 ]4- redox reaction and electrochemical CO2 reduction reaction (CO2 RR) are investigated on the EC-PEIRS platform with a remarkable signal enhancement. Notably, the enhanced IR signals enable a reconstruction of the electrochemical curve of the redox reactions and unveil the CO2 RR mechanism. This study presents a promising technique for boosting the in-depth understanding of interfacial events across diverse applications.

Bio-inspired bimetallic models for electrochemical CO2 reduction.

Inspired by the carbon monoxide dehydrogenase (CODH) active site where two metal ions synergistically catalyze the interconversion between CO2 and CO, we have developed a family of rhenium dipyridine derivatives (1-3), in which potassium 1-aza-18-crown-6-ether (KN18C6) moiety functions as a Lewis acid to assist the CO2 reduction reaction (CO2RR). We found that such design leads to dramatically strong deposition on the electrode under CO2 in the presence of potassium cation, and a clear trend for the deposition rate was observed following the flexibility of linkage between the framework and the KN18C6 moiety; the more flexible, the faster. The origin of deposition was further characterized by a series of control experiments and infrared spectroelectrochemistry (IR-SEC). Unfortunately, the deposition suppresses the subsequent C-O bond cleavage reaction.

New Spectroelectrochemical Insights into Manganese and Rhenium Bipyridine Complexes as Catalysts for the Electrochemical Reduction of Carbon Dioxide.

This study aimed to demonstrate the behavior of different complexes using IR spectroelectrochemistry (SEC), a technique that combines IR spectroscopy with electrochemistry. Four different Mn and Re catalysts for electrochemical CO2 reduction were studied in dry acetonitrile. In the case of Mn(apbpy)(CO)3Br (apbpy = 4(4-aminophenyl)-2,2'-bipyridine), SEC suggested that a very slow catalytic reduction of CO2 also occurs in acetonitrile in the absence of proton donors, but at rather negative potentials. In contrast, the corresponding Re(apbpy)(CO)3Br clearly demonstrated slow catalytic conversion at the first reduction potential. Switching to saturated CO2 solutions in a mixture of acetonitrile and 5% water as a proton donor, the SEC of Mn(apbpy)(CO)3Br displayed a faster catalytic behavior.

Photophysics of Fe-Fe hydrogenase mimic complexes for hydrogen evolution

The photophysical and electrochemical properties of the diiron hydrogenase mimic complex, [Fe2(dpet)(CO)6] (dpet = 1,2-diphenylethene-1,2-dithiol) have been studied using a combination of spectroscopic and electrochemical techniques including cyclic voltammetry, infrared spectroelectrochemistry (IR-SEC), ultrafast transient absorption (TA) spectroscopy and time-resolved infrared spectroscopy (TRIR), with the data interpretation aided by density functional theory (DFT). The complex is a viable catalyst for electrochemical hydrogen evolution, as shown by its electrochemical reversibility and significant increase in the catalytic current upon addition of trifluoroacetic acid (TFA). IR-SEC was used to identify the first and second reduction products, where formation of a bridging μ-CO species was observed. The ultrafast spectroscopy data show that CO loss is only a minor excited state relaxation pathway, unlike other previously reported [FeFe] catalysts, in agreement with steady-state photolysis. The excited state lifetime obtained for this complex (135 ps in DCM and 237 ps in MeCN) is insufficient for [Fe2(dpet)(CO)6] to function as a photocatalyst on its own. However, the photostability of the complex opens up an opportunity for its future use in conjunction with a photosensitiser in photochemical hydrogen evolution.

Solubilizing Metal-Organic Frameworks for an In Situ IR-SEC Study of a CO2 Reduction Catalyst.

Metal-organic frameworks (MOFs) are typically assembled by bridging metal centers with organic linkers for various applications, including providing robust support for heterogeneous catalysts for CO2 reduction. In this study, we have demonstrated the solubilization of a MOF tethered to a CO2-reducing electrocatalyst and studied its fundamental electrochemistry in THF solvent using infrared spectroelectrochemistry (IR-SEC). The fundamental electrochemical properties of this immobilized catalyst were compared to that of its homogeneous counterpart. This approach provides a foundation for future experimental studies to bridge the gap between homogeneous and heterogeneous electrocatalysis.

Electrochemical behavior of fungicide tebuconazole and its voltammetric determination on an oxygen-terminated boron-doped diamond electrode

The first study on electrochemical oxidation of triazole fungicide tebuconazole was performed using an oxygen-terminated boron-doped diamond electrode. The irreversible anodic process occurring at + 1.75 V (vs Ag/AgCl/KCl(sat.)) in 0.1 mol/L HNO3 was studied by cyclic voltammetry, IR spectroelectrochemistry, and density functional theory calculations. The oxidation of tebuconazole leads to the formation of the hydroxylated and dihydroxylated derivatives on the 4-chlorophenyl moiety. Also, the corresponding o-quinone derivative was detected. Further, the anodic signal was used to develop a differential pulse voltammetric method for tebuconazole determination with the following parameters: linear dynamic range from 5.0 × 10−7 to 8.3 × 10−5 mol/L and limit of detection of 1.5 × 10−7 mol/L. The method was successfully applied to the analysis of a commercially available pesticide formulation and model samples of river water after preconcentration of tebuconazole using Amberlite® IRC120 H ion-exchange resin in H+ cycle.

Synthesis of [FeFe] Hydrogenase Mimics with Lipoic acid and its Selenium Analogue as Anchor Groups

Abstract[FeFe] hydrogenase (H2ase) mimicking complexes containing lipoic and selenolipoic acid moieties connected to 2‐hydroxy‐1,3‐dithiopropane and 2‐hydroxy‐1,3‐diselenopropane bridging ligands were synthesized and characterized using different spectroscopic methods. X‐ray diffraction analysis was utilized to determine the molecular structure of a triphenylphosphane substituted analogue. Cyclic voltammetry (CV) investigations on the redox chemistry in presence and absence of acetic acid (AcOH) revealed differing behaviours among the mimics. IR spectroelectrochemistry (IR SEC) enabled deeper insights of structural changes during electrochemical measurements. The elaboration of surface confined systems was studied in preliminary experiments. CV experiments showed that the lipoic acid derivatives of the [FeFe] H2ase mimics formed well‐organized self‐assembled monolayers (SAMs) on Pt electrodes, a promising result for future work.

Manganese Tricarbonyl Diimine Bromide Complexes as Electrocatalysts for Proton Reduction.

Manganese tricarbonyl diimine complexes bearing pyridine and imidazole ligands have been prepared as electrocatalysts for proton reduction using acetic acid as the proton source. The electron-donor ability of the diimine ligand is found to play an important role in determining the efficiency of the electrocatalysts with [MnBr(pybz)(CO)3] (pybz = 2-(2-pyridyl)benzimidazole) exhibiting the lowest overpotential (0.28 V) toward proton reduction. The [Mn(pybz)(CO)3(MeCN)]+ cationic complex prepared via debromination of [MnBr(pybz)(CO)3] by a silver salt has also been shown to catalyze proton reduction upon its electrochemical reduction. A neutral complex [Mn(pyridine-benzimidazolate)(CO)3(MeCN)], which can be synthesized by reacting [MnBr(pybz)(CO)3] with a strong base, has been detected using IR-SEC (infrared spectroelectrochemistry) as an intermediate species in the catalytic process. Using [MnBr(pybz)(CO)3] as the model electrocatalyst, we have carried out density functional calculations to propose a proton reduction mechanism consistent with our experimental observations.

Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt27(CO)31]4- Displaying a Defective Structure.

The molecular Pt nanocluster [Pt27(CO)31]4– (14–) was obtained by thermal decomposition of [Pt15(CO)30]2– in tetrahydrofuran under a H2 atmosphere. The reaction of 14– with increasing amounts of HBF4·Et2O afforded the previously reported [Pt26(CO)32]2– (32–) and [Pt26(CO)32]− (3–). The new nanocluster 14– was characterized by IR and UV–visible spectroscopy, single-crystal X-ray diffraction, direct-current superconducting quantum interference device magnetometry, cyclic voltammetry, IR spectroelectrochemistry (IR SEC), and electrochemical impedance spectroscopy. The cluster displays a cubic-close-packed Pt27 framework generated by the overlapping of four ABCA layers, composed of 3, 7, 11, and 6 atoms, respectively, that encapsulates a fully interstitial Pt4 tetrahedron. One Pt atom is missing within layer 3, and this defect (vacancy) generates local deformations within layers 2 and 3. These local deformations tend to repair the defect (missing atom) and increase the number of Pt–Pt bonding contacts, minimizing the total energy. The cluster 14– is perfectly diamagnetic and displays a rich electrochemical behavior. Indeed, six different oxidation states have been characterized by IR SEC, unraveling the series of 1n– (n = 3–8) isostructural nanoclusters. Computational studies have been carried out to further support the interpretation of the experimental data.

IR spectroelectrochemistry of a heterobimetallic ferrocene-CORM

• Heterobimetallic manganese tricarbonyl-ferrocene complex prepared. • Redox processes studied with cyclic voltammetry (CV). • Reversible redox wave at ferrocene but irreversible ones on manganese centre. • IR spectroelectrochemistry used to study interaction between two metal sites. Heterobimetallic manganese tricarbonyl-ferrocene complex studied with IR spectroelectrochemistry for CO release.

The Effect of Remote Donor Substituents on the Properties of Alkoxy and Amino Fischer Carbene Complexes of Tungsten

AbstractTungsten Fischer ethoxy‐ and dimethylaminocarbene complexes [W{C(X)(C6H4‐4‐R}(CO)5] (X=OEt: series a; or X=NMe2: series b) are synthesized from phenyl substrates containing remote tertiary amino substituents R’2N with R’=Me (2), Ph (3) or C6H4Br‐4 (4). The π‐delocalization and carbene‐stabilizing effects of the distant tertiary amine donor substituent are investigated by NMR and IR spectroscopy, electrochemistry and quantum chemical calculations. A significant transfer of electron density from the remote 4‐R’2N substituent to the carbene C atom in the ethoxycarbene complexes is supported by NMR data and the solid‐state structure of 2 a. This is strongly attenuated in the amino‐substituted carbene complex 2 c and irrelevant in the dimethylaminocarbene complexes of series b, where the electron demand of the electrophilic carbene center is satisfied by the directly attached dimethylamino substituent. Quantum chemical calculations and IR spectroelectrochemistry on complexes 1 a‐‐4 a verify carbene‐centered reductions and a ligand based oxidation of complex 2 b.

Electron-Nuclear Dynamics Accompanying Proton-Coupled Electron Transfer.

Although photoinduced proton-coupled electron transfer (PCET) plays an essential role in photosynthesis, a full understanding of the mechanism is still lacking due to the complex nonequilibrium dynamics arising from the strongly coupled electronic and nuclear degrees of freedom. Here we report the photoinduced PCET dynamics of a biomimetic model system investigated by means of transient IR and two-dimensional electronic-vibrational (2DEV) spectroscopies, IR spectroelectrochemistry (IRSEC), and calculations utilizing long-range-corrected hybrid density functionals. This collective experimental and theoretical effort provides a nuanced picture of the complicated dynamics and synergistic motions involved in photoinduced PCET. In particular, the evolution of the 2DEV line shape, which is highly sensitive to the mixing of vibronic states, is interpreted by accurate computational modeling of the charge separated state and is shown to represent a gradual change in electron density distribution associated with a dihedral twist that occurs on a 120 fs time scale.

Tuning the redox potential of tyrosine-histidine bioinspired assemblies.

Photosynthesis powers our planet and is a source of inspiration for developing artificial constructs mimicking many aspects of the natural energy transducing process. In the complex machinery of photosystem II (PSII), the redox activity of the tyrosine Z (Tyrz) hydrogen-bonded to histidine 190 (His190) is essential for its functions. For example, the Tyrz-His190 pair provides a proton-coupled electron transfer (PCET) pathway that effectively competes against the back-electron transfer reaction and tunes the redox potential of the phenoxyl radical/phenol redox couple ensuring a high net quantum yield of photoinduced charge separation in PSII. Herein, artificial assemblies mimicking both the structural and redox properties of the Tyrz-His190 pair are described. The bioinspired constructs contain a phenol (Tyrz model) covalently linked to a benzimidazole (His190 model) featuring an intramolecular hydrogen bond which closely emulates the one observed in the natural counterpart. Incorporation of electron-withdrawing groups in the benzimidazole moiety systematically changes the intramolecular hydrogen bond strength and modifies the potential of the phenoxyl radical/phenol redox couple over a range of ~ 250mV. Infrared spectroelectrochemistry (IRSEC) demonstrates the associated one-electron, one-proton transfer (E1PT) process upon electrochemical oxidation of the phenol. The present contribution provides insight regarding the factors controlling the redox potential of the phenol and highlights strategies for the design of futures constructs capable of transporting protons across longer distances while maintaining a high potential of the phenoxyl radical/phenol redox couple.