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Extra resources for The Porphyrins. Physical Chemistry, Part A

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Phosphorescence and fluorescence on different scales. From Gouterman and 1 13 Khalil. Table 11 gives some free-base q u a n t u m yields. It can be seen that O f is lower in the free base than for Mg(II), Si(IV), and Sc(III) complexes. Since it appears that Sx —> Tx remains the dominant decay process for Si9 even in the free base, it means that k2 is sizeable without special heavy a t o m enhancement. The short triplet lifetimes of the free-base compared to a number of metallocomplexes (compare Tables 8 and 11) combined with the near absence of phosphorescence in the free base shows that k3 is also sizeable without heavy atom enhancement and perhaps is enhanced by the central 1 hydrogen atoms.

006, 184/60*^isec) [181b]' [162]' [181b]' ? [40] A g ( M 1 0) b References in brackets boldface to (OAP) or lightface to (TPP) data. Emission data in parenthesis are to (OAP) rings, presented as in Table 8. P, L, R: phosphorescent, luminescent, radiationless. P, R together means emission character depends on ligands. c Valence electrons. d Complexes are (OEP)Ru(II)(CO)(py) and (OEP)Os(Il)(NO)(OCH 3). ' Indicates emission references. f (TPP)Ni(III) was reported but without optical d a t a . l b 7 ba * Decay is nonexponential.

Moreover, there are many metalloporphyrins whose absorption and emission spectra have had only minimal study. Since this is the case, our presentation is necessarily incomplete. A. Hypsoporphyrins [Groups VIII, IB] D a t a for the absorption spectra of some hypsoporphyrins has been presented earlier in Figs. 2 and 7 and Tables 5, 6, and 7. F o r the (OEP) and (Etio) rings in vapor, the wavelength of 0(0,0) is less than 570 nm for hypsoporphyrins and greater than 570 nm for normal porphyrins. The Soret band of hypsoporphyrins tend to be similarly blue shifted.

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