Investigation of 1O2 generation by water-soluble α-diimine complexes of platinum(II) and palladium(II) with 3,4-dihydroxybenzoic acid as photosensitizers

Add time:09/04/2019    Source:sciencedirect.com

Eight complexes with the formula [M(NN)(DHBA)] (where MPd(II) or Pt(II), NN is 2,2′-bipyridine (BPY), 2,2′-biquinoline (BIQ), 1,10-phenanthroline (PHEN), 4,7-diphenyl-1,10-phenanthroline (DPP) and DHBA is 3,4-dihydroxybenzoic acid dianion) were found to photosensitize the oxidation of 2,2,6,6-tetramethyl-4-piperidinol (NH) in N,N-dimethylformamide (DMF) to the nitroxide radical. This photo-oxidation reaction involves singlet molecular oxygen (1O2) as an intermediate and its presence was confirmed by quenching studies using bis(diethyldithiocarbamato)nickel(II), as well known 1O2 quencher. The ability of these complexes to photosensitize the above photo-oxidation reaction follows the order, [Pt(PHEN)(DHBA)]·H2O > [Pt(DPP)(DHBA)]·H2O > [Pt(BIQ)(DHBA)] > [Pd(PHEN)(DHBA)] > [Pt(BPY)(DHBA)] > [Pd(DPP)(DHBA)] > [Pd(BPY)(DHBA)]·CH3OH > [Pd(BIQ)(DHBA)]. This order depends on the metal ion, the nature of the α-diimine ligand and the geometry of the metal complex.

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