Visible Light Driven Bromide Oxidation and Ligand Substitution Photochemistry of a Ru Diimine Complex

Li, Guocan; Brady, Matthew D.; Meyer, Gerald J.

doi:10.1021/jacs.8b00944

Cited by 32 publications

(32 citation statements)

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“…211 1 H NMR titrations indicated that the ion-paired bromide was preferentially located next to the ruthenium center. 210 Indeed, resonances associated with 5-H atoms of the 2,2′-bipyrazine ligand and 6-H atoms of the deeb ligand shifted to a larger extent (0.09 and 0.12 ppm, respectively) compared to very small shifts of the 3,3′-H atoms of the 2,2′-bipyrazine ligand. Moving from acetone to CH 2 Cl 2 drastically influenced the ground-and excited-state chemistry.…”

Section: Chemical Reviewsmentioning

confidence: 90%

“…The bromine atom subsequently reacted with Br – to generate Br 2 •– with a rate constant of 1.1 × 10 10 M –1 s –1 . The formal one-electron reduction potential of bromine in acetone was estimated as E °(Br •/– ) = 1.44 ± 0.02 V vs NHE using Marcus theory. , Prolonged irradiation led to the formation of both the cis and trans isomers of [Ru(bpz)(deeb)Br 2 ] that were isolated by column chromatography …”

Section: Halide Photoredox Chemistry With Metal-to-ligand Charge-tran...mentioning

confidence: 99%

“…The formal one-electron reduction potential of bromine in acetone was estimated as E°(Br •/− ) = 1.44 ± 0.02 V vs NHE using Marcus theory. 210,211 Prolonged irradiation led to the formation of both the cis and trans isomers of [Ru(bpz)(deeb)Br 2 ] that were isolated by column chromatography. 210 In acetone, a single equilibrium to yield {[Ru-(bpz) 2 (deeb)] 2+ ,Br − } was determined K eq = 8400 M −1 .…”

Section: Chemical Reviewsmentioning

confidence: 99%

“…210,211 Prolonged irradiation led to the formation of both the cis and trans isomers of [Ru(bpz)(deeb)Br 2 ] that were isolated by column chromatography. 210 In acetone, a single equilibrium to yield {[Ru-(bpz) 2 (deeb)] 2+ ,Br − } was determined K eq = 8400 M −1 . 211 1 H NMR titrations indicated that the ion-paired bromide was preferentially located next to the ruthenium center.…”

Section: Chemical Reviewsmentioning

confidence: 99%

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Halide Photoredox Chemistry

et al. 2019

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Halide photoredox chemistry is of both practical and fundamental interest. Practical applications have largely focused on solar energy conversion with hydrogen gas, through HX splitting, and electrical power generation, in regenerative photoelectrochemical and photovoltaic cells. On a more fundamental level, halide photoredox chemistry provides a unique means to generate and characterize one electron transfer chemistry that is intimately coupled with X−X bond-breaking and -forming reactivity. This review aims to deliver a background on the solution chemistry of I, Br, and Cl that enables readers to understand and utilize the most recent advances in halide photoredox chemistry research. These include reactions initiated through outer-sphere, halide-to-metal, and metal-toligand charge-transfer excited states. Kosower's salt, 1-methylpyridinium iodide, provides an early outer-sphere charge-transfer excited state that reports on solvent polarity. A plethora of new inner-sphere complexes based on transition and main group metal halide complexes that show promise for HX splitting are described. Long-lived charge-transfer excited states that undergo redox reactions with one or more halogen species are detailed. The review concludes with some key goals for future research that promise to direct the field of halide photoredox chemistry to even greater heights. CONTENTS 1. Introduction, Background, and Motivation

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Section: Chemical Reviewsmentioning

confidence: 90%

Section: Halide Photoredox Chemistry With Metal-to-ligand Charge-tran...mentioning

confidence: 99%

Section: Chemical Reviewsmentioning

confidence: 99%

Section: Chemical Reviewsmentioning

confidence: 99%

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Halide Photoredox Chemistry

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“…These methodologies generally involve the formation of charged species. Here, ion pairing plays an important role in solution, as indicated in recent publications [1][2][3][4]. The important role of ion pairing extends in fields like catalysis [5], organic synthesis [6][7][8], and the chemistry of flavonoids [9,10] and radical-induced DNA-strand breaks [11].…”

Section: Introductionmentioning

confidence: 96%

Topological Dynamics of a Radical Ion Pair: Experimental and Computational Assessment at the Relevant Nanosecond Timescale

2020

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Chemical processes mostly happen in fluid environments where reaction partners encounter via diffusion. The bimolecular encounters take place at a nanosecond time scale. The chemical environment (e.g., solvent molecules, (counter)ions) has a decisive influence on the reactivity as it determines the contact time between two molecules and affects the energetics. For understanding reactivity at an atomic level and at the appropriate dynamic time scale, it is crucial to combine matching experimental and theoretical data. Here, we have utilized all-atom molecular-dynamics simulations for accessing the key time scale (nanoseconds) using a QM/MM-Hamiltonian. Ion pairs consisting of a radical ion and its counterion are ideal systems to assess the theoretical predictions because they reflect dynamics at an appropriate time scale when studied by temperature-dependent EPR spectroscopy. We have investigated a diketone radical anion with its tetra-ethylammonium counterion. We have established a funnel-like transition path connecting two (equivalent) complexation sites. The agreement between the molecular-dynamics simulation and the experimental data presents a new paradigm for ion–ion interactions. This study exemplarily demonstrates the impact of the molecular environment on the topological states of reaction intermediates and how these states can be consistently elucidated through the combination of theory and experiment. We anticipate that our findings will contribute to the prediction of bimolecular transformations in the condensed phase with relevance to chemical synthesis, polymers, and biological activity.

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Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

et al. 2019

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Photoactive metal complexes employing Earthabundant metal ions are ak ey to sustainable photophysical and photochemical applications.W ee xploit the effects of an inversion center and ligand non-innocence to tune the luminescence and photochemistry of the excited state of the [CrN 6 ] chromophore [Cr(tpe) 2 ] 3+ with close to octahedral symmetry (tpe = 1,1,1-tris(pyrid-2-yl)ethane). [Cr(tpe) 2 ] 3+ exhibits the longest luminescence lifetime (t = 4500 ms) reported up to date for am olecular polypyridyl chromium(III) complex together with av ery high luminescence quantum yield of F = 8.2 %a t room temperature in fluid solution. Furthermore,t he tpe ligands in [Cr(tpe) 2 ] 3+ are redox non-innocent, leading to reversible reductive chemistry.The excited state redoxpotential and lifetime of [Cr(tpe) 2 ] 3+ surpass those of the classical photosensitizer [Ru(bpy) 3 ] 2+ (bpy = 2,2'-bipyridine) enabling energy transfer (to oxygen) and photoredox processes (with azulene and tri(n-butyl)amine).Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.

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Visible Light Driven Bromide Oxidation and Ligand Substitution Photochemistry of a Ru Diimine Complex

Cited by 32 publications

References 59 publications

Halide Photoredox Chemistry

Halide Photoredox Chemistry

Topological Dynamics of a Radical Ion Pair: Experimental and Computational Assessment at the Relevant Nanosecond Timescale

Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

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