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Query: UMLS:C0220723 (
PCA
)
4,687
document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)
New mono- and dinuclear rhenium(I) tricarbonyls, of formulas [Re(bpy)(CO)3(
PCA
)]+ (1), [(bpy)(CO)3Re(I)(
PCA
)Re(I)(CO)3(bpy)]2+ (2), and [(bpy)(CO)3Re(I)(
PCA
)Ru(II)(NH3)5]3+ (3) (bpy = 2,2'-bipyridine,
PCA
= 4-pyridinecarboxaldehydeazine), have been synthesized as
PF6
- salts and characterized by spectroscopic, electrochemical, and photophysical techniques. These species do not emit at room temperature in CH(3)CN; however, in aqueous solutions, a decrease in pH induces luminescence in all of them, due to protonation of one of the N atoms of the -C=N-N=C- chain of
PCA
, as indicated by the pKa values of the ground states, obtained by absorption measurements, which are ca. 3 orders of magnitude lower than the pKa value of the pyridine N of
PCA
in complex 1. On the other hand, the values of pKa* of the excited states, obtained by emission measurements, of complexes 1 and 2 are similar (pKa* = 2.7 +/- 0.1 at I = 0.1 M) and higher than those of the corresponding ground states. At low values of pH, chemical decomposition takes place rapidly in complex 3, but not in 1 and 2, supporting the possible use of these latter species as luminescent sensors of pH. The heterodinuclear complex, of formula [(bpy)(CO)3Re(I)(
PCA
)Ru(III)(NH3)5]4+, was obtained by bromine oxidation of the [Re(I), Ru(II)] precursor in CH3CN solution; from spectral and electrochemical measurements, the recombination charge-transfer reaction [Re(II), Ru(II) ] --> [Re(I), Ru(III)], which occurs after photoexcitation, is predicted to lie in the Marcus inverted region.
...
PMID:Proton-induced luminescence of mono- and dinuclear rhenium(I) tricarbonyl complexes containing 4-pyridinealdazine. 1690 46