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Bis(2,2 prime -bipyridine)ruthenium(II)-hexacyanochromate(III) chromophore-luminophore complexes. Intramolecular energy transfer, excited-state intervalence transfer, and doublet-doublet annihilation

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00196a028· OSTI ID:6707264
; ;  [1]
  1. Centro di Fotochimica CNR, Ferrara (Italy)
The binuclear (NC-Ru(bpy){sub 2}-NC-Cr(CN){sub 5}){sup 2{minus}} and trinuclear ((CN){sub 5}Cr-CN-Ru(bpy){sub 2}-NC-Cr(CN){sub 5}){sup 4{minus}} bimetallic complexes have been synthesized and their photophysical behavior has been studied. Visible light absorption by the Ru(bpy){sub 2}{sup 2+} chromophore leads to phosphorescence from the Cr(CN){sub 6}{sup 3{minus}} luminophore. The results demonstrate the occurrence of a fast ({tau} < 10 ns), efficient ({eta} = 1) intramolecular exchange energy transfer process from the MLCT triplet of the Ru(II) fragment to the doublet state of the Cr(CN){sub 6}{sup 3{minus}} fragment. Distinctive features of these chromophore-luminophore complexes with respect t the behavior of the isolated luminophore are as follows: (i) large light-harvesting efficiency (antenna effect); (ii) response to visible light (spectral sensitization); (iii) 100% efficient population of the emitting state; (iv) photostability. Intramolecular processes of the same type are probably responsible for the failure to observe doubly excited species upon two-photon excitation of the trinuclear complex.
OSTI ID:
6707264
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:14; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English