Excited-state Redox Potentials Research Articles

Unveiling N-Fused Nitreniums as Potent Catalytic Photooxidants.

The first example of a hitherto-unknown facet of catalytic photooxidant capability of nitrenium cations is reported herein. The fundamental limitation of inability of the traditional and reported nitreniums to achieve the excited-state redox potential beyond +2.0 V (vs Ag/AgCl), the primary requirement for a powerful photooxidant, is addressed in this work by developing a structurally unique class of N-fused nitrenium cations, with the required structural engineering involving extensive π-conjugation through ring fusion at the nitrenium site, which enabled significant lowering of the LUMO energy and easy reduction at the excited state (excited-state redox potential up to +2.5 V vs Ag/AgCl), facilitated by effective delocalization/stabilization of the generated radical. This finding opens a new way to discover novel and useful (photo)catalytic properties of nitrenium cations beyond just Lewis acidity.

Photocatalytic Reduction of CO2 into CO with Cyclometalated Pt(II) Complexes of N^C^N Pincer Dipyridylbenzene Ligands: A DFT Study.

In this work, density functional theory (DFT) calculations were employed to study the photocatalytic reduction of CO2 into CO using a series of Pt(II) square planar complexes with the general formula [Pt(5-R-dpb)Cl] (dpb = 1,3-di(2-pyridyl)benzene anion, R = H, N,N-dimethylaniline,T thiophene, diazaborinine). The CO2-into-CO conversion process is thought to proceed via two main steps, namely the photocatalytic/reduction step and the main catalytic step. The simulated absorption spectra exhibit strong bands in the range 280-460 nm of the UV-Vis region. Reductive quenching of the T1 state of the complexes under study is expected to be favorable since the calculated excited state redox potentials for the reaction with sacrificial electron donors are highly positive. The redox potentials reveal that the reductive quenching of the T1 state, important to the overall process, could be modulated by suitable changes in the N^C^N pincer ligands. The CO2 fixation and activation by the three coordinated Pt(II) catalytically active species are predicted to be favorable, with the Pt-CO2 bond dissociation energies D0 in the range of -36.9--10.3 kcal/mol. The nature of the Pt-CO2 bond of the Pt(II) square planar intermediates is complex, with covalent, hyperconjugative and H-bonding interactions prevailing over the repulsive electrostatic interactions. The main catalytic cycle is estimated to be a favorable exergonic process.

Diindolocarbazole-Based Rigid Donor-Acceptor TADF Molecules for Energy and Electron Transfer Photocatalysis.

The design and synthesis of four twisted donor-acceptor (D-A) thermally activated delayed fluorescence (TADF) molecules CBZ-IQ, CBZ-2FIQ, DI-IQ and DI-2FIQ is reported in this work based on diindolocarbazole (DI) and phenyl carbazole as donor and indoloquinoxalines as acceptor. These compounds serve as photocatalysts for organic transformations. Theoretical calculations and experimental data showed reasonable singlet and triplet energy gaps of 0.17-0.26 eV for all compounds. All molecules showed increase in fluorescence quantum yields after degassing the solution and the transient photoluminescence decay showed two components: shorter prompt components (11.4 ns to 31 ns) and longer delayed components (36.4 ns to 1.5 μs) which further indicate the occurrence of TADF process. Cyclic voltammetry studies indicated well-suited excited state redox potentials of all compounds to catalyze organic transformations such as heteroarene arylation. Accordingly, photocatalytic C-H arylation of heteroarenes were performed using these compounds with excellent isolated yields of upto 80 %. Due to their suitable efficient triplet energy levels, all the emitters were also employed as energy transfer photocatalysts in E to Z isomerization of stilbene with the excellent conversion of ~90 %.

Unveiling the potency of a phenalenyl-based photocatalyst for intramolecular dehydrogenative lactonization

Here, an intramolecular dehydrogenative lactonization reaction has been accomplished using a phenalenyl-based organic photocatalyst.

Isocyanides as Catalytic Electron Acceptors in the Visible Light Promoted Oxidative Formation of Benzyl and Acyl Radicals.

The recent disclosure of the ability of aromatic isocyanides to harvest visible light and act as single electron acceptors when reacting with tertiary aromatic amines has triggered a renewed interest in their application to the development of green photoredox catalytic methodologies. Accordingly, the present work explores their ability to promote the generation of both alkyl and acyl radicals starting from radical precursors such as Hantzsch esters, potassium alkyltrifluoroborates, and α-oxoacids. Mechanistic studies involving UV-visible absorption and fluorescence experiments, electrochemical measurements of the ground-state redox potentials along with computational calculations of both the ground- and the excited-state redox potentials of a set of nine different aromatic isocyanides provided key insights to promote a rationale design of a new generation of isocyanide-based organic photoredox catalysts. Importantly, the green potential of the investigated chemistry has been herein demonstrated by a direct and easy access to deuterium labeled compounds.

Synthesis of Soluble Quinacridone Photocatalysts for the Homogeneous Oxidation of Thioethers

AbstractEvaluation of quinacridone (QA) derivatives as homogeneous metal‐free photocatalysts is here presented. QA derivatives were synthetized and systematically characterized, measuring their ground state and excited state redox potentials in dichloromethane (DCM) and 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP), in order to understand how structural modifications influenced their photocatalytic properties. In particular, the effect of dicyanomethylene and nitro EWG groups was investigated, in order to develop a photocatalyst capable of promoting oxidative processes in the presence of molecular oxygen. Among the analyzed derivatives, 2,9‐dinitro‐N,N′‐dibutylquinacridone (DNDBQA) was the one with the highest excited state reduction potential (Ered*=1.60 V in HFIP vs SCE), while N,N’‐dibutylquinacridone (DBQA) showed valuable excited state redox potentials (Ered*=1.29 V; Eox*=−1.28 V in HFIP vs SCE), making it suitable for bimodal applications in oxidative and reductive photocatalytic processes. Afterwards, the synthetized QA derivatives were examined as photocatalysts to promote the selective aerobic oxidation of thioether to sulfoxide. Promising results in thioanisole oxidation were achieved with all the QA derivatives tested as photocatalysts, in terms of yield and selectivity. Remarkably, DBQA showed the best performances, catalyzing the reaction in only 20 minutes, using 0.5 % of the photocatalyst, and showing excellent performances in the oxidation of several thioether derivatives.

Prediction of Redox Power for Photocatalysts: Synergistic Combination of DFT and Machine Learning.

The accurate prediction of excited state properties is a key element of rational photocatalyst design. This involves the prediction of ground and excited state redox potentials, for which an accurate description of electronic structures is needed. Even with highly sophisticated computational approaches, however, a number of difficulties arise from the complexity of excited state redox potentials, as they require the calculation of the corresponding ground state redox potentials and the estimation of the 0-0 transition energies (E0,0). In this study, we have systematically evaluated the performance of DFT methods for these quantities on a set of 37 organic photocatalysts representing 9 different chromophore scaffolds. We have found that the ground state redox potentials can be predicted with reasonable accuracy that can be further improved by rationally minimizing the systematic underestimations. The challenging part is to obtain E0,0, as calculating it directly is highly demanding and its accuracy depends strongly on the DFT functional employed. We have found that approximating E0,0 with appropriately scaled vertical absorption energies offers the best compromise between accuracy and computational effort. An even more accurate and cost-effective approach, however, is to predict E0,0 with machine learning and avoid the use of DFT for excited state calculations. Indeed, the best excited state redox potential predictions are achieved with the combination of M062X for ground state redox potentials and machine learning (ML) for E0,0. With this protocol, the excited state redox potential windows of the photocatalyst frameworks could be adequately predicted. This shows the potential of combining DFT with ML in the computational design of photocatalysts with preferred photochemical properties.

Metal Ion-Linked Molecular Multilayers on Inorganic Substrates: Structure and Applications

Metal ion-linked multilayers have emerged as a simple and modular means of assembling molecular components on an inorganic substrate. The choice of molecules, based on their excited state energies and redox potentials, has enabled the directional control of energy and electron transfer events for application in electrochromics, solar energy harvesting, molecular rectifiers, photocatalysis, and more. Here, we recount the more than 35-year journey of metal ion-linked multilayers and their transition from planar to mesoporous substrates and from homogeneous to heterogeneous multilayers. This includes showcasing the vast range of components (i.e., substrates, metal ions, and molecules), structural insights, and applications. We also highlight current limitations in our knowledge of and ability to control these systems which must be overcome to realize the full potential of metal ion-linked multilayers.

Impact of Bidentate Pyridyl-Mesoionic Carbene Ligands: Structural, (Spectro)Electrochemical, Photophysical, and Theoretical Investigations on Ruthenium(II) Complexes.

We present here new synthetic strategies for the isolation of a series of Ru(II) complexes with pyridyl-mesoionic carbene ligands (MIC) of the 1,2,3-triazole-5-ylidene type, in which the bpy ligands (bpy = 2,2'-bipyridine) of the archetypical [Ru(bpy)3]2+ have been successively replaced by one, two, or three pyridyl-MIC ligands. Three new complexes have been isolated and investigated via NMR spectroscopy and single-crystal X-ray diffraction analysis. The incorporation of one MIC unit shifts the potential of the metal-centered oxidation about 160 mV to more cathodic potential in cyclic voltammetry, demonstrating the extraordinary σ-donor ability of the pyridyl-MIC ligand, while the π-acceptor capacities are dominated by the bpy ligand, as indicated by electron paramagnetic resonance spectroelectrochemistry (EPR-SEC). The replacement of all bpy ligands by the pyridyl-MIC ligand results in an anoidic shift of the ligand-centered reduction by 390 mV compared to the well-established [Ru(bpy)3]2+ complex. In addition, UV/vis/NIR-SEC in combination with theoretical calculations provided detailed insights into the electronic structures of the respective redox states, taking into account the total number of pyridyl-MIC ligands incorporated in the Ru(II) complexes. The luminescence quantum yield and lifetimes were determined by time-resolved absorption and emission spectroscopy. An estimation of the excited state redox potentials conclusively showed that the pyridyl-MIC ligand can tune the photoredox activity of the isolated complexes to stronger photoreductants. These observations can provide new strategies for the design of photocatalysts and photosensitizers based on MICs.

Iron Photoredox Catalysis-Past, Present, and Future.

Photoredox catalysis of organic reactions driven by iron has attracted substantial attention throughout recent years, due to potential environmental and economic benefits. In this Perspective, three major strategies were identified that have been employed to date to achieve reactivities comparable to the successful noble metal photoredox catalysis: (1) Direct replacement of a noble metal center by iron in archetypal polypyridyl complexes, resulting in a metal-centered photofunctional state. (2) In situ generation of photoactive complexes by substrate coordination where the reactions are driven via intramolecular electron transfer involving charge-transfer states, for example, through visible-light-induced homolysis. (3) Improving the excited-state lifetimes and redox potentials of the charge-transfer states of iron complexes through new ligand design. We seek to give an overview and evaluation of recent developments in this rapidly growing field and, at the same time, provide an outlook on the future of iron-based photoredox catalysis.

Unveiling Photodegradation and Photosensitization Mechanisms of Unconjugated Pterins.

Unconjugated pterins are ubiquitous molecules participating in countless enzymatic processes and potentially involved in the photosensitization of singlet oxygen, amino acids, and nucleotides. Following electronic excitation with UV-A light, some of these pterins degrade, producing hydrogen peroxide as the main side product. This process, that is known to take place in vivo, contributes to oxidative stress and melanocyte destruction in vitiligo. In this work, we present for the first time mechanistic insight to the formation of transient triplet species which simultaneously trigger Type I and Type II photosensitizing processes and the initiation of degradation processes. Our calculations reveal that photodegradation of 6-biopterin, which accumulates in the skin of vitiligo patients, leads to 6-formylpterin via retro-aldol reaction, and subsequently to 6-carboxypterin through a water-mediated aldehyde oxidation. Additionally, we show that the changes in the photosensitizing potential of these systems with pH come from the modulation of their excited-state redox potentials.

Visible‐Light Induced Fixation of SO2 into Organic Molecules with Polypyridine Chromium(III) Complexes

AbstractIncorporation of sulfur dioxide into organic compounds is achieved by a photocatalytic approach using sensitizers made from earth‐abundant chromium(III) ions and visible light leading to sulfones and sulfonamides. We employed three different chromium(III) sensitizers [Cr(ddpd)2]3+, [Cr(bpmp)2]3+ and [Cr(tpe)2]3+ with long excited state lifetimes and different ground and excited state redox potentials as well as varying stability under the reaction conditions (ddpd=N,N’‐dimethyl‐N,N’‐dipyridin‐2‐yl‐pyridine‐2,6‐diamine; bpmp=2,6‐bis(2‐pyridylmethyl)pyridine; tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). Key reaction steps of the catalytic cycles are identified by electrochemical, luminescence quenching, photolysis, laser flash photolysis and catalytic experiments delivering a detailed picture of the challenges in these transformations. The reactivity of the reduced chromium complex was identified as a key property to explain the reaction outcomes. Initial cage escape yield determinations with [Cr(tpe)2]3+ revealed that desired photoreactions occur with unusually high quantum efficiencies, whereas side reactions are almost unproductive.

Quantitative prediction of excited-state decay rates for radical anion photocatalysts.

We present a computational approach for predicting key properties of organic radical anions, including excited-state lifetimes and redox potentials. The approach shows good agreement with experimental data and has potential for in silico screening to facilitate the rational design of photocatalysts.

Balancing Panchromatic Absorption and Multistep Charge Separation in a Compact Molecular Architecture

A panchromatic triad and a charge-separation unit are joined in a crossbar architecture to capture solar energy. The panchromatic-absorber triad (T) is comprised of a central free-base porphyrin that is strongly coupled via direct ethyne linkages to two perylene-monoimide (PMI) groups. The charge-separation unit incorporates a free-base or zinc chlorin (C or ZnC) as a hole acceptor (or electron donor) and a perylene-diimide (PDI) as an electron acceptor, both attached to the porphyrin via diphenylethyne linkers. The free-base porphyrin is common to both light-harvesting and charge-separation motifs. The chlorin and PDI also function as ancillary light absorbers, complementing direct excitation of the panchromatic triad to produce the discrete lowest excited state of the array (T*). Attainment of full charge separation across the pentad entails two steps: (1) an initial excited-state hole/electron-transfer process to oxidize the chlorin (and reduce the panchromatic triad) or reduce the PDI (and oxidize the panchromatic triad); and (2) subsequent ground-state electron/hole migration to produce oxidized chlorin and reduced PDI. Full charge separation for pentad ZnC-T-PDI to generate ZnC+-T-PDI- occurs with a quantum yield of ∼30% and mean lifetime ∼1 μs in dimethyl sulfoxide. For C-T-PDI, initial charge separation is followed by rapid charge recombination. The molecular designs and studies reported here reveal the challenges of balancing the demands for charge separation (linker length and composition, excited-state energies, redox potentials, and medium polarity) with the constraints for panchromatic absorption (strong electronic coupling of the porphyrin and two PMI units) for integrated function in solar-energy conversion.

Tuning the Photocatalytic Performance of Ruthenium(II) Polypyridine Complexes Via Ligand Modification for Visible-Light-Induced Phosphorylation of Tertiary Aliphatic Amines.

Tuning the redox potential of commonly available photocatalyst to improve the catalytic performance or expand its scope for challenging synthetic conversions is an ongoing demand in synthetic chemistry. Herein, the excited state properties and redox potential of commercially available [Ru(bpy)3 ]2+ photocatalyst were tuned by modifying the structure of the bipyridine ligands with electron-donating/withdrawing units. The visible-light-mediated photoredox phosphorylation of tertiary aliphatic amines was demonstrated under mild conditions. A series of cross-dehydrogenative coupling reactions were performed employing the RuII complexes as photocatalyst giving the corresponding α-aminophosphinoxides and α-aminophosphonates via carbon-phosphorus (C-P) bond formation.

Tuning the Ground- and Excited-State Redox Potentials of Octahedral Hexanuclear Rhenium(III) Complexes by the Combination of Terminal Halide and N-Heteroaromatic Ligands.

The present study reports that the ground- and excited-state Re6(23e)/Re6(24e) redox potentials of an octahedral hexanuclear rhenium(III) complex can be controlled by systematically changing the number and type of the N-heteroaromatic ligand (L) and the number of chloride ions at the six terminal positions. Photoirradiation of [Re6(μ3-S)8Cl6]4– with an excess amount of L afforded a mono-L-substituted hexanuclear rhenium(III) complex, [Re6(μ3-S)8Cl5(L)]3– (L = 4-dimethylaminopyridine (dmap), 3,5-lutidine (lut), 4-methylpyridine (mpy), pyridine (py), 4,4′-bipyridine (bpy), 4-cyanopyridine (cpy), and pyrazine (pz)). The bis- and tris-lut-substituted complexes, trans- and cis-[Re6(μ3-S)8Cl4(lut)2]2– and mer-[Re6(μ3-S)8Cl3(lut)3]−, were synthesized by the reaction of [Re6(μ3-S)8Cl6]3– with an excess amount of lut in refluxed N,N-dimethylformamide. The mono-L-substituted complexes showed one-electron redox processes assignable to E1/2[Re6(23e)/Re6(24e)] = 0.49–0.58 V versus Ag/AgCl. The ground-state oxidation potentials were linearly correlated with the pKa of the N-heteroaromatic ligand [pKa(L)], the 1H NMR chemical shift of the ortho proton on the coordinating ligand, and the Hammett constant (σ) of the pyridyl-ligand substituent. The series of [Re6(μ3-S)8X6–n(L)n]n−4 complexes (n = 0, X = Cl, Br, I, or NCS; n = 1–3, X = Cl) showed a linear correlation with the sum of the Lever electrochemical parameters at the six terminal ligands (ΣEL). The cyclic voltammograms of the mono-L-substituted complexes (L = bpy, cpy, and pz) showed one-electron redox waves assignable to E1/2(L0/L–) = −1.28 to −1.48 V versus Ag/AgCl. Two types of photoluminescences were observed for the complexes, originating from the cluster core-centered excited triplet state (3CC) for L = dmap, lut, mpy, and py and from the metal-to-ligand charge-transfer excited triplet state (3MLCT) for L = bpy, cpy, and pz. The complexes with the 3CC character exhibited emission features and photophysical properties similar to those of ordinary hexanuclear rhenium complexes. The emission maximum wavelength of the complexes with 3MLCT shifted to the longer wavelength in the order L = 4-phenylpyridine (ppy), bpy, pz, and cpy, which agreed with the difference between E1/2[Re6(23e)/Re6(24e)] and E1/2(L0/L–). The calculated oxidation potential of the excited hexanuclear rhenium complex with the 3CC character was linearly correlated with pKa(L), σ, and ΣEL. The ground- and excited-state oxidation potentials were finely tuned by the combination of halide and L ligands at the terminal positions.

Triphenylamine-based cadmium coordination polymer as a heterogeneous photocatalyst for visible-light-driven α-alkylation of aldehydes

The ingenious design of photoredox ligand is crucial to regulate the photoabsorption and redox potential of coordination polymer-based photocatalysts. Herein, by suitable modifying the photoactive triphenylamine, a propeller-like ligand tris(3′-carboxybiphenyl)amine (H3TCBA) was synthesized and used to construct a photofunctional Cd(II)-based coordination polymer, Cd-TCBA, with visible-light absorption band and negative enough excited state redox potential of −2.24 ​V. The good photoelectric performances promote Cd-TCBA to work as heterogeneous photocatalyst for photocatalytic α-alkylation of aldehydes with a high catalytic yield up to 89%. The high stability makes Cd-TCBA readily be recycled and reused at least five times without significant performance loss. The partially deprotonated HTCBA2− in Cd-TCBA not only creates suitable acidic/basic environment but also forms effective hydrogen bond interactions towards diethyl-2-bromomalonate substrate as donor, accelerating the electron transfer from excited state Cd-TCBA∗ to substrate and the formation of enamine intermediates, finally achieving efficient coupling of photoredox and organocatalytic cycles. In addition, the possible catalytic mechanisms were also investigated.

Tuning the Electrochemical and Photophysical Properties of Osmium-Based Photoredox Catalysts

AbstractThe use of low-energy deep-red (DR) and near-infrared (NIR) light to excite chromophores enables catalysis to ensue across barriers such as materials and tissues. Herein, we report the detailed photophysical characterization of a library of OsII polypyridyl photosensitizers that absorb low-energy light. By tuning ligand scaffold and electron density, we access a range of synthetically useful excited state energies and redox potentials.1 Introduction1.1 Scope1.2 Measuring Ground-State Redox Potentials1.3 Measuring Photophysical Properties1.4 Synthesis of Osmium Complexes2 Properties of Osmium Complexes2.1 Redox Potentials of Os(L)2-Type Complexes2.2 Redox Potentials of Os(L)3-Type Complexes2.3 UV/Vis Absorption and Emission Spectroscopy3 Conclusions

A Photoreactive Iron(II) Complex Luminophore.

Controlling the order and lifetimes of electronically excited states is essential to effective light-to-potential energy conversion by molecular chromophores. This work reports a luminescent and photoreactive iron(II) complex, the first performant group homologue of prototypical sensitizers of ruthenium. Double cyclometalation of a phenylphenanthroline framework at iron(II) favors the population of a triplet metal-to-ligand charge transfer (3MLCT) state as the lowest energy excited state. Near-infrared (NIR) luminescence exhibits a monoexponential decay with τ = 2.4 ns in the solid state and 1 ns in liquid phase. Lifetimes of 14 ns at 77 K are in line with a narrowing of the NIR emission band at λem,max = 1170-1230 nm. Featuring a 3MLCT excited-state redox potential of -2 V vs the ferrocene/ferrocenium couple, the use of the Fe(II) chromophore as a sensitizer for light-driven synthesis is exemplified by the radical cross-coupling of 4-chlorobromobenzene and benzene.

Photoinduced Charge Transfer with a Small Driving Force Facilitated by Exciplex-like Complex Formation in Metal-Organic Frameworks.

Photoinduced charge transfer (PCT) is a key step in the light-harvesting (LH) process producing the redox equivalents for energy conversion. However, like traditional macromolecular donor-acceptor assemblies, most MOF-derived LH systems are designed with a large ΔG0 to drive PCT. To emulate the functionality of the reaction center of the natural LH complex that drives PCT within a pair of identical chromophores producing charge carriers with maximum potentials, we prepared two electronically diverse carboxy-terminated zinc porphyrins, BFBP(Zn)-COOH and TFP(Zn)-COOH, and installed them into the hexagonal pores of NU-1000 via solvent-assisted ligand incorporation (SALI), resulting in BFBP(Zn)@NU-1000 and TFP(Zn)@NU-1000 compositions. Varying the number of trifluoromethyl groups at the porphyrin core, we tuned the ground-state redox potentials of the porphyrins within ca. 0.1 V relative to that of NU-1000, defining a small ΔG0 for PCT. For BFBP(Zn)@NU-1000, the relative ground- and excited-state redox potentials of the components facilitate an energy transfer (EnT) from NU-1000* to BFBP(Zn), forming BFBP(Zn)S1* which entails a long-lived charge-separated complex formed through an exciplex-like [BFBP(Zn)S1*-TBAPy] intermediate. Various time-resolved spectroscopic data suggest that EnT from NU-1000* may not involve a fast Förster-like resonance energy transfer (FRET) but rather through a slow [NU-1000*-BFBP(Zn)] intermediate formation. In contrast, TFP(Zn)@NU-1000 displays an efficient EnT from NU-1000* to [TFP(Zn)-TBAPy], a complex that formed at the ground state through electronic interaction, and thereon showed the excited-state feature of [TFP(Zn)-TBAPy]*. The results will help to develop synthetic LHC systems that can produce long-lived photogenerated charge carriers with high potentials, i.e., high open-circuit voltage in photoelectrochemical setups.