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Issue 47, 2014
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Ultrafast spectroscopy and structural characterization of a photochromic isomerizing ruthenium bis-sulfoxide complex

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Abstract

Irradiation of [Ru(bpy)2(bpSOp)](PF6)2 (where bpy is 2,2′-bipyridine and bpSOp is 1,3-bis(phenylsulfinyl)propane) results in the formation of two new isomers, namely the S,O- and O,O-bonded species. The crystal structure of the bis-thioether and bis-sulfoxide complexes are reported. NMR spectroscopy of the bis-thioether complex in solution is consistent with the molecular structure determined by diffraction methods. Further, NMR spectroscopy of the bis-sulfoxide complex reveals two conformers in solution, one that is consistent with the solid state structure and a second conformer showing distortion in the aliphatic portion of the chelate ring. Time-resolved visible absorption spectroscopy reveals isomerization time constants of 91 ps in dichloroethane (DCE) and 229 ps in propylene carbonate (PC). Aggregate isomerization quantum yields of 0.57 and 0.42 have been determined in DCE and in PC, respectively. The kinetics of the thermal reversion from the O,O- to S,O-bonded isomer are strongly solvent dependent, occurring with rates of 2.41 × 10−3 and 4.39 × 10−5 s−1 in DCE, and 4.68 × 10−4 and 9.79 × 10−6 s−1 in PC. The two kinetic components are assigned to the two isomers identified in solution.

Graphical abstract: Ultrafast spectroscopy and structural characterization of a photochromic isomerizing ruthenium bis-sulfoxide complex

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Publication details

The article was received on 13 May 2014, accepted on 22 Sep 2014 and first published on 23 Sep 2014


Article type: Paper
DOI: 10.1039/C4DT01402B
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Dalton Trans., 2014,43, 17847-17855

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    Ultrafast spectroscopy and structural characterization of a photochromic isomerizing ruthenium bis-sulfoxide complex

    A. W. King, J. P. Malizia, J. T. Engle, C. J. Ziegler and J. J. Rack, Dalton Trans., 2014, 43, 17847
    DOI: 10.1039/C4DT01402B

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