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

doi:10.1021/jacs.8b00944

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

Abstract

We report the complex [Ru(deeb)(bpz)₂]²⁺ (RuBPZ²⁺, deeb = 4,4'-diethylester-2,2'-bipyridine, bpz = 2,2'-bipyrazine) forms a single ion pair with bromide, [RuBPZ²⁺, Br^–]⁺, with K_eq = 8400 ± 200 M^–1 in acetone. The RuBPZ²⁺ displayed photoluminescence (PL) at room temperature with a lifetime of 1.75 μs. The addition of bromide to a RuBPZ²⁺ acetone solution led to significant PL quenching and Stern–Volmer plots showed upward curvature. Time-resolved PL measurements identified two excited state quenching pathways, static and dynamic, which were operative toward [RuBPZ²⁺, Br^–]⁺ and free RuBPZ²⁺, respectively. The single ion-pair [RuBPZ²⁺, Br^–]⁺* had a lifetime of 45 ± 5 ns, consistent with an electron transfer rate constant, k_et = (2.2 ± 0.3) × 10⁷ s^–1. In contrast, RuBPZ²⁺* was dynamically quenched by bromide with a quenching rate constant, k_q = (8.1 ± 0.1) × 10¹⁰ M^–1 s^–1. Nanosecond transient absorption revealed that both the static and dynamic pathways yielded RuBPZ⁺ and Br₂^•– products that underwent recombination to regenerate the ground state with a second-order rate constant, k_cr = (2.3 ± 0.5) × 10¹⁰ M^–1 s^–1. Kinetic analysis revealed that RuBPZ⁺ was a primary photoproduct, while Br₂^•– was secondary product formed by the reaction of a Br^• with Br^–, k = (1.1more »« less

Authors:

^[1]; Brady, Matthew D. ^[1];

^[1]

Univ. of North Carolina, Chapel Hill, NC (United States)

Publication Date:: 2018-03-29

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1470297

Grant/Contract Number:: SC0001011

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 140; Journal Issue: 16; Related Information: UNC partners with University of North Carolina (lead); Duke University; University of Florida; Georgia Institute of Technology; University; North Carolina Central University; Research Triangle Institute; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (photovoltaic); solar (fuels); photosynthesis (natural and artificial); hydrogen and fuel cells; electrodes - solar; charge transport; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)

Citation Formats


                    Li, Guocan, Brady, Matthew D., and Meyer, Gerald J. Visible Light Driven Bromide Oxidation and Ligand Substitution Photochemistry of a Ru Diimine Complex.  United States: N. p., 2018. 
        Web.  doi:10.1021/jacs.8b00944.

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                    Li, Guocan, Brady, Matthew D., & Meyer, Gerald J. Visible Light Driven Bromide Oxidation and Ligand Substitution Photochemistry of a Ru Diimine Complex.  United States.  doi:10.1021/jacs.8b00944.

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                    Li, Guocan, Brady, Matthew D., and Meyer, Gerald J. Thu .  
        "Visible Light Driven Bromide Oxidation and Ligand Substitution Photochemistry of a Ru Diimine Complex".  United States.  doi:10.1021/jacs.8b00944.  https://www.osti.gov/servlets/purl/1470297.

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@article{osti_1470297,

  title        = {Visible Light Driven Bromide Oxidation and Ligand Substitution Photochemistry of a Ru Diimine Complex},

  author       = {Li, Guocan and Brady, Matthew D. and Meyer, Gerald J.},

  abstractNote = {We report the complex [Ru(deeb)(bpz)2]2+ (RuBPZ2+, deeb = 4,4'-diethylester-2,2'-bipyridine, bpz = 2,2'-bipyrazine) forms a single ion pair with bromide, [RuBPZ2+, Br–]+, with Keq = 8400 ± 200 M–1 in acetone. The RuBPZ2+ displayed photoluminescence (PL) at room temperature with a lifetime of 1.75 μs. The addition of bromide to a RuBPZ2+ acetone solution led to significant PL quenching and Stern–Volmer plots showed upward curvature. Time-resolved PL measurements identified two excited state quenching pathways, static and dynamic, which were operative toward [RuBPZ2+, Br–]+ and free RuBPZ2+, respectively. The single ion-pair [RuBPZ2+, Br–]+* had a lifetime of 45 ± 5 ns, consistent with an electron transfer rate constant, ket = (2.2 ± 0.3) × 107 s–1. In contrast, RuBPZ2+* was dynamically quenched by bromide with a quenching rate constant, kq = (8.1 ± 0.1) × 1010 M–1 s–1. Nanosecond transient absorption revealed that both the static and dynamic pathways yielded RuBPZ+ and Br2•– products that underwent recombination to regenerate the ground state with a second-order rate constant, kcr = (2.3 ± 0.5) × 1010 M–1 s–1. Kinetic analysis revealed that RuBPZ+ was a primary photoproduct, while Br2•– was secondary product formed by the reaction of a Br• with Br–, k = (1.1 ± 0.2) × 1010 M–1 s–1. Marcus theory afforded an estimate of the formal reduction potential for E0(Br•/–) in acetone, 1.42 V vs NHE. A 1H NMR analysis indicated that the ion-paired bromide was preferentially situated close to the RuII center. Prolonged steady state photolysis of RuBPZ2+ and bromide yielded two ligand-substituted photoproducts, cis- and trans-Ru(deeb)(bpz)Br2. Finally, a photochemical intermediate, proposed to be [Ru(deeb)(bpz)(κ1-bpz)(Br)]+, was found to absorb a second photon to yield cis- and trans-Ru(deeb)(bpz)Br2 photoproducts.},

  doi          = {10.1021/jacs.8b00944},

  journal      = {Journal of the American Chemical Society},

  number       = 16,

  volume       = 140,

  place        = {United States},

  year         = {2018},

  month        = {3}

}

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DOI: 10.1021/jacs.8b00944

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Works referencing / citing this record:

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

Abstract

Citation Formats

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