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Synthesis and photophysical characterization of highly luminescent complexes of Ru(II) containing 4,4′-di-(p-carboxyphenyl)-2,2′-bipyridine

✍ Scribed by K. Kalyanasundaram; Md.K. Nazeeruddin; M. Grätzel; G. Viscardi; P. Savarino; E. Barni

Publisher
Elsevier Science
Year
1992
Tongue
English
Weight
915 KB
Volume
198-200
Category
Article
ISSN
0020-1693

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✦ Synopsis

The synthesis and photophysical characterization of several complexes of Ru(I1) containing 4,4'-di(carboxyphenyl)-2,2'-bipyridine (DCPB) and related bipyridine ligands are reported. In all complexes studied the lowest excited state is associated with Ru-,DCPB charge transfer (CT) transition. The introduction of phenyl groups between the peripheral carboxyl group and the bipyridine framework caused a red-shifted, more intense absorption but the excited state properties (luminescence and transient absorption) remain nearly the same. The acid-base properties in the ground and excited state are different. With respect to 4,4'-carboxy-2,2'-bipyridine (dcbpy) derivative, the ground state pK, of Ru(DCPB),

increases by about 2.5 pH units and a further extremely small increase in the pK, is observed upon visible light excitation. The results suggest that the charge density is largely localized in the diimine unit and does not carry through the phenyl group. This could account for inefficient sensitization (< 8% monochromatic photon-to-current conversion efficiency) obtained on TiOz electrodes. Possible implication of the present results on the design of photosensitizers is also discussed.

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