Laser flash photolysis of 7-(piperazin-1-yl) fluoroquinolones leads to the formation of a triplet excited state (3A*) at the end of the pulse (lambdamax 520, 610, and 620 nm for enoxacin, ciprofloxacin, and norfloxacin, respectively). Phosphate and bicarbonate buffers react with 3A* to form a secondary triplet (3B*, reaction rates (0.8-9.9) x 108 M-1 s-1), whose T-T absorption is red-shifted (lambdamax 670 nm for enoxacin, 700 nm for ciprofloxacin and norfloxacin). The formation of a secondary triplet is not a common process and disagrees with previous work suggesting that electron transfer occurs between phosphate buffer and the primary triplet excited state with the formation of the anion radical of the fluoroquinolone (FQ.-). We have shown that the FQ.- transient absorption spectrum is quite distinct from that of 3B*. The photophysical characteristics of 3B* have been determined by energy transfer to naproxen, and it has been found that its energy is lower than that of 3A*.
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