Synthesis, spectroscopy and photochemistry of dyads and triads with porphyrins and bis(terpyridine)ruthenium(II) complex

Prashanth Kumar Poddutoori, Premaladha Poddutoori, Bhaskar G. Maiya

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7 Scopus citations

Abstract

A bis(terpyridine)ruthenium(II) complex ([Ru]2+) was covalently connected via a floppy -OCH2CH2O- spacer to the free-base porphyrin (H) or zinc(II) porphyrin (Zn) or both, to obtain dyads ([HRu] 2+, [ZnRu]2+) and triads ([HRuH]2+, [ZnRuH]2+, [ZnRuZn]2+). These compounds have been fully characterized by MALDI, UV-vis, 1H NMR (1D and 1H- 1H COSY) spectroscopies, and also by the cyclic and differential pulse voltammetric techniques. Absorption spectroscopy of these newly synthesized compounds shows that significant exciton coupling exists in non-polar solvents (cyclohexane and toluene) between the porphyrin ring and the bis(terpyridine)ruthenium(II) complex. Upon excitation within the Soret band of [HRu]2+/[HRuH]2+, free-base porphyrin fluorescence was found to be strongly quenched in non-polar and weakly quenched in polar solvents, probably due to 'singlet-triplet' energy transfer from the free-base porphyrin to the [Ru]2+ complex. Whereas, in [ZnRu] 2+/[ZnRuZn]2+, zinc(II) porphyrin fluorescence was quantitatively and reasonably quenched in non-polar and polar solvents, respectively by mainly electron transfer from the zinc(II) porphyrin to the [Ru]2+ complex. The solvent plays a crucial role in the photophysical properties of these compounds, since the energy of the triplet metal-to-ligand charge-transfer (3MLCT) excited state is influenced by the polarity of the medium. Finally, [ZnRuH]2+ exhibits the combined fluorescence properties of [HRu]2+ and [ZnRu]2+ but the observed additional quenching in non-polar solvents for the zinc(II) porphyrin component is explained by energy transfer from the zinc(II) porphyrin to the free-base porphyrin and/or the bis(terpyridine)ruthenium(II) complex.

Original languageEnglish (US)
Pages (from-to)1049-1060
Number of pages12
JournalJournal of Porphyrins and Phthalocyanines
Volume10
Issue number8
DOIs
StatePublished - 2006

Keywords

  • Bis(terpyridine)ruthenium(II) complex
  • Electron transfer
  • Energy transfer
  • Non-polar and polar solvents
  • Porphyrin

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