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Dirhodium(II,II) Complexes as Red-Light Absorbing Photosensitizers and as Catalysts for Photocatalytic Proton Reduction

Sayre, Hannah J
http://orcid.org/0000-0002-3214-4899
http://rave.ohiolink.edu/etdc/view?acc_num=osu1531910584052025

Abstract Details

2018, Doctor of Philosophy, Ohio State University, Chemistry.
Harvesting and storing solar energy is necessary to continue meeting global energy demands. New dirhodium(II,II) complexes have been developed as broad-spectrum photosensitizers with tunable oxidative and reductive quenching mechanisms. In the presence of a sacrificial electron donor, methyl viologen dication electron relay and colloidal Pt(0) catalyst, cis-Rh2(DTolF)2(npCOO)2 (DTolF = p-di-tolylformamidinate; npCOO = 2-carboxylate-1,8-naphthyridine) photosensitizes catalytic proton reduction via an oxidative quenching mechanism upon irr = 655 nm. Under identical conditions, cis-[Rh2(DTolF)2(qnnp)2][BF4]2 (qnnp = 1,8-naphthyridine-2-quinoline) is a light absorber for photocatalytic proton reduction and proceeds via a reductive quenching mechanism. Evolved H2 with cis-Rh2(DTolF)2(npCOO)2 and cis-[Rh2(DTolF)2(qnnp)2][BF4]2 photosensitizers was 0.31 umol (2 TON) and 0.54 umol (4 TON), respectively, in this system with irr = 655 nm. Evolved H2 using the prototypical [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) photosensitizer in this system with irr = 447 nm was 0.40 umol (3 TON). Dirhodium(II,II) photosensitizers were modified for coordination to TiO2 nanoparticles and electron injection into the conduction band was observed by TRIR spectroscopy. Dirhodium(II,II) complexes were also developed as proton reduction catalysts both electrochemically and photochemically. The structural considerations for improving the design of dirhodium(II,II) catalysts have been investigated.
Claudia Turro, PhD (Advisor)
Hannah Shafaat, PhD (Committee Member)
Casey Wade, PhD (Committee Member)
149 p.
Chemistry
Photocatalysis, Proton Reduction, Red Light Absorber, Dirhodium

Recommended Citations

Citations

  • Sayre, H. J. (2018). Dirhodium(II,II) Complexes as Red-Light Absorbing Photosensitizers and as Catalysts for Photocatalytic Proton Reduction [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1531910584052025

    APA Style (7th edition)

  • Sayre, Hannah. Dirhodium(II,II) Complexes as Red-Light Absorbing Photosensitizers and as Catalysts for Photocatalytic Proton Reduction. 2018. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1531910584052025.

    MLA Style (8th edition)

  • Sayre, Hannah. "Dirhodium(II,II) Complexes as Red-Light Absorbing Photosensitizers and as Catalysts for Photocatalytic Proton Reduction." Doctoral dissertation, Ohio State University, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=osu1531910584052025

    Chicago Manual of Style (17th edition)

osu1531910584052025
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