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Controlling the Helicity of 2,2‘-Bipyridyl Ruthenium(II) and Zinc(II) Hemicage Complexes

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    Controlling the Helicity of 2,2‘-Bipyridyl Ruthenium(II) and Zinc(II) Hemicage Complexes
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    Contribution from the Department of Chemistry, Princeton University, Princeton, New Jersey 08544
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2007, 129, 1, 210–217
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    https://doi.org/10.1021/ja067016v
    Published December 9, 2006
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    Abstract

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    Two enantiomers of a new 4,5-pineno-2,2‘-bipyridine ligand were synthesized and subsequently incorporated into hemicage ligands through a phenyl linker to yield ligands (+)-L1 and (−)-L1 or through a mesityl linker to yield ligands (+)-L2 and (−)-L2. Complexation of these ligands to Ru(II) afforded diastereomerically pure Δ and Λ isomers, as verified through circular dichroism and circularly polarized luminescence spectroscopy. Ligands (+)-L2 and (−)-L2 were further coordinated to Zn(II) to form a complex with intriguing photophysical properties. Whereas Zn(bpy)32+ was shown to be a fluorescent emitter outside the visible spectrum, the caging process provided an unprecedented enhancement of intersystem crossing and subsequent switching to the phosphorescent emission of blue light. Additionally, the chiroptical properties of the Zn(II) complexes were also studied.

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    Complete citation for ref 29 as well as NMR and mass spectrometry data for key metal compounds. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cite this: J. Am. Chem. Soc. 2007, 129, 1, 210–217
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