* To whom correspondence should be addressed.
Received October 19, 1998; Revision received January 20, 1999
The interaction of dimeric forms of meso-tetraphenylporphine with Mn2+ as well as the interaction of associated forms of meso-tetra(p-aminophenyl)porphine bound to a hydrophobic--hydrophilic copolymer with Mn2+ and Fe3+ were studied by absorption, luminescence, Raman, and EPR spectroscopies. Both dimeric and associated forms of these porphyrins produced Mn2+ complexes. Manganese ions in these complexes undergo clusterization, which is accompanied by transformation of the six-line EPR signal of Mn2+ into a broad single-line signal. The EPR signal of Mn2+ in these clusters is characterized by a g-factor value typical of a free electron with half-width DeltaHpp = 50 mT. The interaction of the two-component complex with Fe3+ produces a donor--acceptor complex. The electronic spectrum of the donor--acceptor complex contains a broad band with a maximum at 760 nm. The molar extinction coefficient of the complex at 760 nm is 9.1·104 M-1·cm-1, and the rate constant for its formation is Kdac = (3.9 ± 0.6)·106 M-1. The constants for Mn2+ binding to the organic compounds used in this work were also determined.
KEY WORDS: porphyrin associates, hydrophobic--hydrophilic copolymer, ions of transition metals