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Structural, Spectroscopic, and Kinetic Investigation of Modified Photochromic Ruthenium Sulfoxide Complexes

Malizia, Jason Patrick

Abstract Details

2014, Bachelor of Science (BS), Ohio University, Chemistry.
The complexes [Ru(bpy)2(bpSOp)](PF6)2 (bpSOp = 1,3-bis(phenylsulfinyl)propane), [Ru(bpy)2(bpSOb)](PF6)2 (bpSOb = 1,4-bis(phenylsulfinyl)butane), [Ru(bpy)2(PhSOEtSPh)](PF6)2 (PhSOEtSPh = 2-(phenylsulfinyl)ethylsulfanylbenzene), and [Ru(bpy)2(PhSOEtSePh)](PF6)2 (PhSOEtSePh = 2-(phenylsulfinyl)ethylselenobenzene) were synthesized and investigated by a number of techniques. The structure of these complexes were characterized by 1D and 2D NMR along with X-ray crystallography. Electrochemical measurements were performed on monosulfoxide metal complexes and S to O linkage isomerization was found to occur after oxidation of ruthenium(II) to ruthenium(III). MLCT irradiation of the complexes in solution in conjunction with electronic absorption measurements have shown that the monosulfoxide complexes undergo S to O linkage isomerization and the bissulfoxide complexes undergo SS to SO and SS to OO isomerization upon absorption of a single photon. It has been shown that small or simple modifications to the sulfoxide chelate in polypyridyl ruthenium sulfoxides lead to dramatic changes in the ground and excited state dynamics and kinetics of these complexes. Specifically, increasing the size of the chelating ring of a bidentate sulfoxide ligand through the insertion of a methylene group has been shown to increase the efficacy and speed of isomerization while the chemical nature of the 2nd donor atom in a bidentate sulfoxide ligand plays a pivotal role in the observed photophysics and photochemistry of these complexes.
Jeffrey Rack, Ph D (Advisor)
267 p.

Recommended Citations

Citations

  • Malizia, J. P. (2014). Structural, Spectroscopic, and Kinetic Investigation of Modified Photochromic Ruthenium Sulfoxide Complexes [Undergraduate thesis, Ohio University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ouhonors1398971012

    APA Style (7th edition)

  • Malizia, Jason. Structural, Spectroscopic, and Kinetic Investigation of Modified Photochromic Ruthenium Sulfoxide Complexes. 2014. Ohio University, Undergraduate thesis. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ouhonors1398971012.

    MLA Style (8th edition)

  • Malizia, Jason. "Structural, Spectroscopic, and Kinetic Investigation of Modified Photochromic Ruthenium Sulfoxide Complexes." Undergraduate thesis, Ohio University, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=ouhonors1398971012

    Chicago Manual of Style (17th edition)