Author : Jason Patrick Malizia
Publisher :
ISBN 13 :
Total Pages : 267 pages
Book Rating : 4.:/5 (114 download)
Book Synopsis Structural, Spectroscopic, and Kinetic Investigation of Modified Photochromic Ruthenium Sulfoxide Complexes by : Jason Patrick Malizia
Download or read book Structural, Spectroscopic, and Kinetic Investigation of Modified Photochromic Ruthenium Sulfoxide Complexes written by Jason Patrick Malizia and published by . This book was released on 2014 with total page 267 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.