Platinum-porphyrin complexes

The first reported porphyrin complexes of platinum(IV) date from 1980 and were obtained by hydrogen peroxide oxidation of platinum(II) porphyrin complexes in an acidic medium (HC1).479 Since then oxidation of platinum(II) complexes of other porphyrins has been achieved by the same method,480 and by chlorine,481 or bromine482 oxidation. Reaction with iodine did not lead to oxidation and treatment of platinum(IV) porphyrin complexes with iodide resulted in reduction to platinum(II). 

The Soret, a and j3 bands in the visible spectra of platinum(IV) porphyrin complexes occur at longer wavelengths than their platinum(II) analogues,482 H NMR resonances are all shifted downfield,482 the 13C resonances of the a carbons are shifted upheld, and the H-195Pt and 13C-195Pt coupling constants are reduced.480 Whereas excitation of platinum(II) porphyrin complexes... 

Like the palladium(II) complexes, the platinum(II) porphyrins show appreciable phosphorescence even in aqueous media at room temperature in one study,169 singlet oxygen quantum yields ranged from 0.1 to 0.9 and were strongly influenced by dimerization/aggregation. Platinum(II) 5,10,15,20-tetrakis(/>-carboxyphenyl)porphyrin and platinum(II)coproporphyrin-I ((36) for Pd read Pt) have been studied as phosphorescent labels of antibodies for use in time-resolved microscopy.189... 

For example, in 1963 the photochemistry of magnesium phthalocyanine with coordinated uranium cations was studied in pyridine and ethanol and indicated the occurrence of PET to the uranium complex . A rapid photoinduced electron transfer (2-20 ps) followed by an ultrafast charge recombination was shown for various zinc and magnesium porphyrins linked to a platinum terpyridine acetylide complex . The results indicated the electronic interactions between the porphyrin subunit and the platinum complex, and underscored the potential of the linking para-phenylene bisacetylene bridge to mediate a rapid electron transfer over a long donor-acceptor distance. 

Platinum porphyrin complexes can be prepared by reaction with PtCl2(PhCN)2. Purification of the final complex is by medium pressure liquid chromatography on alumina. The strongly phosphorescent platinum(II) porphyrin complexes are efficient sensitizers for stilbene isomerization. The quantum yields for the cis to trans process are greater than unity because of a quantum chain process in which the metalloporphyrin serves both as an energy donor and an acceptor.1110 Picosecond laser spectroscopy has been used to obtain time-resolved excited-state spectra of platinum octaethylporphyrin complexes, and to probe the excited-state energy levels.1111 Tetrabenzoporphyrin complexes have been prepared for platinum in both the divalent and tetravalent oxidation states. The divalent complex shows strong phosphorescence at 745 nm.1112... 

For example, platinum(II) porphyrins are perhaps the oldest known class of luminescent Pt(II) complexes. They emit deep into the red region (e.g. =... 

C, 546 nm) in a linear range from 0 to 180 mm Hg is comparable to oxygen sensors containing palladium(II) or platinum(ll) porphyrin complexes. 

Supramolecular systems assembled by peripheral and axial coordination were also thoroughly described. For example, heteroarrays held by axial coordination, particularly of zinc, nickel, ruthenium, tin, silicon, etc. porphyrins and phthalo-cyanines to peripheral pyridyl and 4,4-bipyridyl groups were described. Another interesting class of compounds are porphyrin dimers prepared by coordinative assembly of cw- icso-(4-pyridyl)porphyrins with PdCla forming two [PtCl2(pyP)2] complexes, and more complex tesselated structures by substitution of the platinum complex chloro ligands by 2,3-diamine(azaporphyrins), as depicted in Fig. 12. 

Fig. 15 Scheme showing the stmcture of mthenium porphyrins axially bond to platinum complexes... 

With their preference for square planar coordination, palladium(II) and platinum(II) are well suited to binding to porphyrins and related N4 donor macrocycles. Therefore, Pd(octaethylporphyrin) is readily synthesized starting from the labile PhCN complex (like the platinum analogue) [92]... 

Table 2 summarizes these data for metal complexes of the porphyrin series which appear at present to be most relevant to PDT. Apart from the platinum(II) example, there is a reasonable correlation between this empirical 5 and stability class within each oxidation number. 

Since Fenton s work in the late nineteenth century, the role of transition metals in oxygen chemistry is known, but the formation of oxygen adducts with coordination metal complexes and their importance for O2 activation have been studied much later [1, 97]. The lively interest in ORR catalysis comes from its utmost importance to the development of fuel cells and this justifies that only a few studies have been done with metal complexes in solution most have been devoted to carbon electrodes modified by immobilization of a catalyst. The research for good catalysts that could be efficient substitutes for the expensive platinum naturally moved toward porphyrins. 

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