Direct attachment of putative electron acceptors ((bi)pyridinium ions) to either Ru(bpy)3 2+ or Ru(1,10-phenanthroline)3 2+ (excellent photo-excited-state electron donors) leads to enhancement of excited-state lifetimes, rather than the diminution anticipated from electron transfer quenching. An evaluation of photo redox and emission energetics suggests that charged “quencher” attachment lengthens luminescence lifetimes by (a) diminishing the reductant strength of the photo excited state, (b) inhibiting intersystem crossing to a short-lived d−d state, and/or (c) diminishing Franck−Condon factors for nonradiative decay.

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