Extended porphyrins. New IR phosphors for oxygen measurements

Tetrabenzoporphyrins (TBP) of Zn, Pd, Lu, Y, Sn and Pb show strong absorption bands in the near IR region of the spectrum. Phosphorescence in dimethylformamide (DMF) solutions at room temperature was measured for Pd and Lu complexes giving quantum yields of 7.9% and 3.5% and lifetimes of 250 microseconds and 870 microseconds, respectively. Pd meso-tetraphenyltetrabenzoporphyrin 1 (PdPh4TBP) shows a red shift of the absorption Q-band to 628 nm. 1 reacted with ClSO3H and obtained chlorosulfonato derivative 2 was converted to a set of water soluble chromophores: Pd meso-tetra(sulfophenyl)tetrabenzoporphyrin (Pd Ph4(SO3Na)4TBP) 3, corresponding sulfonamide (Pd Ph4(PEG)4TBP) 4 with aminopolyethyleneglycol (Av.M.W. 5,000) and sulfonamide derivatives of glucoseamine (Pd Ph4(glucoseamine)4TBP) 5 and aminophenylacetic acid (Pd Ph4(phenac)4TBP) 6. Electronic absorption and phosphorescence spectra of 1 and some of its derivatives were recorded and phosphorescence quantum yields and lifetimes were measured for deoxygenated solutions. The oxygen quenching constants were measured for the water soluble complexes 3 and 4 and found to be suitable for oxygen measurements in vivo. Tetranaphthaloporphyrin (TNP) complexes of Pd and Lu as well as Pd meso-tetraphenyltetranaphthaloporphyrin (PdPh4TNP) were synthesized and their absorption and emission properties were examined.