Porphyrins characteristics

The porphyrin ring system (the parent compound 1 is also known as porphin) consists of four pyrrole-type subunits joined by four methine ( = CH-) bridges to give a macrotetracycle. The macrocycle contains 227i-electrons from which 1871-electrons form a delocalized aromatic system according to Huckel s 4n + 2 rule for aromaticity. The aromaticity of the porphyrin determines the characteristic physical and chemical properties of this class of compounds. The aromatic character of porphyrins has been confirmed by determination of their heats of combustion.1"3 X-ray investigations4 of numerous porphyrins have shown the planarity of the nucleus which is a prerequisite for the aromatic character. 

All the known porphyrin isomers are typical benzoid aromatic compounds which show distinctly porphyrin-like characteristic electronic absorption spectra.13 Also the complexation properties for metal ions, NH tautomerism and the NMR spectra are quite similar to the parent porphyrin structure. 

The electronic absorption spectra of the products of one-electron electrochemical reduction of the iron(III) phenyl porphyrin complexes have characteristics of both iron(II) porphyrin and iron(III) porphyrin radical anion species, and an electronic structure involving both re.sonance forms Fe"(Por)Ph] and tFe "(Por—)Ph has been propo.sed. Chemical reduction of Fe(TPP)R to the iron(II) anion Fe(TPP)R) (R = Et or /7-Pr) was achieved using Li BHEt3 or K(BH(i-Bu)3 as the reductant in benzene/THF solution at room temperature in the dark. The resonances of the -propyl group in the F NMR spectrum of Fe(TPP)(rt-Pr) appear in the upfield positions (—0.5 to —6.0 ppm) expected for a diamagnetic porphyrin complex. This contrasts with the paramagnetic, 5 = 2 spin state observed... 

Alkyliron(lll) porphyrin complexes are air. sensitive, and when exposed to oxygen under ambient conditions the products are the very stable iron(IIl) /t-oxo dimers, [Fe(Por)]20. A more careful investigation revealed that the reaction of the alkyl complexes with oxygen proceeds via insertion of O2 into the Fe—C bond. " When a solution of Fe(Por)R (R = Me, Et, i-Pr) is exposed to O2 at —70 C, the characteristic H NMR spectrum of the low spin iron alkyl complex disappears and is replaced by a new, high spin species. The same species can be generated from the reaction of an alkyl hydroperoxide with Fe(Por)OH, and is formulated as... 

The various porphyrinogens are colorless, whereas the various porphyrins are all colored. In the smdy of porphyrins or porphyrin derivatives, the characteristic absorption spectrum that each exhibits—in both the visible and the ultraviolet regions of the spectrum—is of great value. An example is the absorption curve for a solution of porphyrin in 5% hydrochloric acid (Figure 32-10). Note particularly the sharp absorption band near 400 nm. This is a distinguishing feamre of the porphin ring and is characteristic of all porphyrins regardless of the... 

When porphyrins dissolved in strong mineral acids or in organic solvents are illuminated by ultraviolet hght, they emit a strong red fluorescence. This fluorescence is so characteristic that it is often used to detect small amounts of free porphyrins. The double bonds joining the pyrrole rings in the porphyrins are responsible for the characteristic absorption and fluorescence of these compounds these double bonds are absent in the porphyrinogens. 

That dendrimers are unique when compared with other architectures is confirmed by an investigation on porphyrin core dendrimers and their isomeric linear analogues [63]. The isomers displayed dramatically different hydrodynamic properties, crystallinity, and solubility characteristics when compared to those of their dendritic analogues, and photophysical studies showed that energy transfer from the poly(benzylether) backbone to the core was more efficient in the dendrimer because of the shorter distance between the donor units and the acceptor core. 

Simple Fe porphyrins whose catalytic behavior in the ORR has been smdied fairly extensively are shown in Fig. 18.9. Literature reports disagree substantially in quantitative characterization of the catalytic behavior overpotential, stability of the catalysts, pH dependence, etc.). It seems plausible that in different studies the same Fe porphyrin possesses different axial hgation, which depends on the electrolyte and possibly specific residues on the electrode surface the thicknesses and morphologies of catalytic films may also differ among studies. AU of these factors may contribute to the variabUity of quantitative characteristics. The effect of the supporting surface on... 

Despite the potential impact of novel photosynthetic routes based on these developments, the most ambitious application remains in the conversion of solar energy into electricity. Dvorak et al. showed that photocurrent as well as photopotential response can be developed across liquid-liquid junctions during photoinduced ET reactions [157,158]. The first analysis of the output power of a porphyrin-sensitized water-DCE interface has been recently reported [87]. Characteristic photocurrent-photovoltage curves for this junction connected in series to an external load are displayed in Fig. 22. It should be mentioned that negligible photoresponses are observed when only the platinum counterelectrodes are illuminated. Considering irradiation AM 1, solar energy conversions from 0.01 to 0.1% have been estimated, with fill factors around 0.4. The low conversion... 

Imamura (11,20,21) synthesized several similar perpendicular dimers exploiting axial coordination of the 4-pyridyl free-base porphyrin to Ru(II)CO (3) and Os(II)CO (4) porphyrins (Fig. 1). The pyridine-ruthenium and pyridine-osmium interactions are much stronger than the pyridine-zinc interaction, and the complexes are perfectly stable in solution and can be isolated by precipitation. One of the ruthenium dimers was characterized by FAB-MS (11). Complexation is accompanied by characteristic changes in JH NMR chemical shift, indicating... 

Anderson has produced a range of improved zinc porphyrin-DABCO ladder complexes where an aromatic substituent in the meso position reduces aggregation (57). The 1H NMR spectra show a characteristic... 

Hunter (60) reported a self-assembled open polymer formed by a zinc porphyrin bearing one para-aniline substituent at the meso position. The ortho- and mela-analogs discussed above form closed dimers, but the geometry of the para-derivative precludes this, and polymerization is the only alternative (76, Fig. 31). Although the dilution experiments could be fitted to a non-cooperative polymerization model with a pairwise association constant (K = 190 M 1) practically identical to that found for simple aniline-zinc porphyrin complexes (K = 130 M 1), broadening of the 4H NMR spectrum at high concentrations is characteristic of oligomerization. 

As discussed in section 2.2, a mixture of AMP and AA showed two solid condensed phases above and below about 30 mN m- [5,10]. A loosely stacked structure of two porphyrins was proposed for LB films prepared at higher surface pressures than 30 mNmr1, which was caused by squeezing-out of a monomolecular structure formed at lower surface pressure [5,10]. In this section, photoelectric characteristics of LB films containing AMP and AA deposited at two solid condensed phases will be discussed in relation to multilayer structure and the anisotropic intermolecular tunneling rates [87]. Seven monolayers of 1 5 or 1 10 mixture of AMP and AA were deposited at 20 and 50 mN m-1 on an ITO plate at 18 °C to form stable Y-type LB films. Aluminum was vacuum evaporated onto LB films as sandwich-type electrodes at 10-6 Torr. Steady photocurrents were measured in a similar manner as mentioned above. 

The structure of HRP-I has been identified as an Fe(IV) porphyrin -ir-cation radical by a variety of spectroscopic methods (71-74). The oxidized forms of HRP present differences in their visible absorption spectra (75-77). These distinct spectral characteristics of HRP have made this a very useful redox protein for studying one-electron transfers in alkaloid reactions. An example is illustrated in Fig. 2 where the one-electron oxidation of vindoline is followed by observing the oxidation of native HRP (curve A) with equimolar H202 to HRP-compound I (curve B). Addition of vindoline to the reaction mixture yields the absorption spectrum of HRP-compound II (curve C) (78). This methodology can yield useful information on the stoichiometry and kinetics of electron transfer from an alkaloid substrate to HRP. Several excellent reviews on the properties, mechanism, and oxidation states of peroxidases have been published (79-81). 

E. Wang, C. Romero, D. Santiago and V. Syntilas, Optical anion sensing characteristics of indium-porphyrin and lipophilic dichlorofluorescein doped polymer films, Anal. Chim. Acta, 433 (2001) 89-95. 

So far, catalytic systems in which the mediator plays the role of both catalyst and electron carrier have been considered. Figure 4.21 shows an example where these two roles are dissociated.21 The catalyst, in the sense of a chemical catalyst, is the Co(II) porphyrin embedded in the Nafion (a trademark of Dupont) film, while the electron are shuttled by the ruthenium hexamine 3 + /2+ couple attached electrostatically to the Nafion backbone. The catalytic reaction now involves two successive steps, as expected for a chemical catalysis process (see Sections 4.2.1 and 4.3.1), calling for the definition of two characteristic currents. One has the same... 

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