**2. The chemical characteristics of porphyrins**

The synthetic world of porphyrins is extremely rich and its history began in the middle of 1930s. An enormous number of synthetic procedures have been reported until now, and the reason can be easily understood analysing the porphyrin skeleton. In principle, there are many chemical strategies to synthesized porphyrins, involving different building blocks, like pyrroles, aldehydes, dipyrromethanes, dipyrromethenes, tripyrranes and linear tetrapyrroles.

The most famous monopyrrole polymerization route to obtain porphyrins involves the synthesis of tetraphenyl porphyrins, from reaction between pyrrole and benzaldehyde (Atwood et al., 1996). This procedure was first developed by Rothemund (Rothemund, 1935) and, after modification by Adler, Longo and colleagues (Adler et al., 1967), was finally optimized by Lindsey's group (Lindsey et al.,1987). In the Rothemund and Adler/Longo methodology the crude product contains between 5 and 10% of a byproduct, discovered later to be the *meso*-tetraphenylchlorin which is converted in the product under oxidative conditions (Fig. 2).

Rothemund in 1935 set up the synthesis of porphyrins in one step by reaction of benzaldehyde and pyrrole in pyridine in a sealed flask at 150 °C for 24 h but the yields were low, and the experimental conditions so severe that few benzaldehydes could be converted to the corresponding substituted porphyrin (Rothemund, 1936; Menotti, 1941). The reason in the low yield is that the main by-product of reaction was *meso*substituted chlorin and in understanding the nature of its formation, Calvin and coworkers (Calvin et al., 1946)

The porphyrins play important roles in the nature, due to their special absorption, emission, charge transfer and complexing properties as a result of their characteristic ring structure of

As to their electronic absorption, they display extreme intense bands, the so-called Soret or B-bands in the 380–500 nm range with molar extinction coefficients of 105 M-1 cm-1. Moreover, at longer wavelengths, in the 500–750-nm range, their spectra contain a set of weaker, but still considerably intense Q bands with molar extinction coefficients of 104 M-1 cm-1. Thus, their absorption bands significantly overlap with the emission spectrum of the solar radiation reaching the biosphere, resulting in efficient tools for conversion of radiation to chemical energy. In such a conversion, the favourable emission and energy transfer properties of porphyrin derivatives are indispensable as in the case of chlorophylls, which contain magnesium ion in the core of the macrocycle. Also, metalloporphyrins can be utilized in artificial photosynthetic systems, modelling the most important function of the

The studies of the wavelength shift of their adsorption band and the absorbance changes as function of pH, temperature, solvent change, reaction with metal ions and other parameters permits to obtained accurate information about equilibrium, complexation, kinetic and

This review, resumes the best successes in the use of spectrophotometer UV-Vis for explained the chemical characteristics of this extraordinary group of natural occurring

The synthetic world of porphyrins is extremely rich and its history began in the middle of 1930s. An enormous number of synthetic procedures have been reported until now, and the reason can be easily understood analysing the porphyrin skeleton. In principle, there are many chemical strategies to synthesized porphyrins, involving different building blocks, like pyrroles, aldehydes, dipyrromethanes, dipyrromethenes, tripyrranes and linear

The most famous monopyrrole polymerization route to obtain porphyrins involves the synthesis of tetraphenyl porphyrins, from reaction between pyrrole and benzaldehyde (Atwood et al., 1996). This procedure was first developed by Rothemund (Rothemund, 1935) and, after modification by Adler, Longo and colleagues (Adler et al., 1967), was finally optimized by Lindsey's group (Lindsey et al.,1987). In the Rothemund and Adler/Longo methodology the crude product contains between 5 and 10% of a byproduct, discovered later to be the *meso*-tetraphenylchlorin which is converted in the product under oxidative

Rothemund in 1935 set up the synthesis of porphyrins in one step by reaction of benzaldehyde and pyrrole in pyridine in a sealed flask at 150 °C for 24 h but the yields were low, and the experimental conditions so severe that few benzaldehydes could be converted to the corresponding substituted porphyrin (Rothemund, 1936; Menotti, 1941). The reason in the low yield is that the main by-product of reaction was *meso*substituted chlorin and in understanding the nature of its formation, Calvin and coworkers (Calvin et al., 1946)

molecules and clarifies the potential of these molecules in many fields of application.

conjugated double bonds (Rest et al.,1982).

green plants (Harriman et al., 1996).

**2. The chemical characteristics of porphyrins** 

aggregation of porphyrins.

tetrapyrroles.

conditions (Fig. 2).

discovered that the addition of metal salts to the reaction mixture, such as zinc acetate, increases the yield of porphyrin from 4-5% for the free-base derivative, and decreases the amount of chlorin compound. Others improvement were obtained by changing opportunely the reaction conditions and substituents in benzaldehyde molecule framework.

Fig. 2. Synthesis of 5,10,15,20-tetraphenyl porphyrin.

Adler, Longo and coworkers, in the 1960s (Adler et al. 1967), re-examined the synthesis of *meso*substituted porphyrins and developed an alternative approach (Fig. 3) with a method that involves an acid catalyzed pyrrole aldehyde condensation in glassware open to the atmosphere in the presence of air. The reactions were carried out at high temperature, in different solvents and concentrations range of reactants with a yields of 30-40%, and with chlorin contamination lower than that obtained with the Rothemund synthesis.

Fig. 3. Adler-Longo method for preparing *meso*-substituted porphyrins.

Over the period 1979-1986, Lindsey developed a new and innovative two-step room temperature method to synthesize porphyrins, motivated by the need for more gentle conditions for the condensation of aldehydes and pyrrole, in order to enlarge the number of the aldehydes utilizable and then the porphyrins available (Anderson et al., 1990; Acheson et al., 1976; Dailey, 1990; Porra, 1997; Mauzarall, 1960). The method has been a new strategy for the synthesis of porphyrins, using a sequential process of condensation and oxidation steps. The reactions were carried out under mild conditions in an attempt to achieve equilibrium during condensation, and to avoid side reactions in all steps of the porphyrinforming process (Fig. 4)

The porphyrin macrocycle is a highly-conjugated molecule containing 22 -electrons, but only 18 of them are delocalized according to the Hückel's rule of aromaticity (4n+2 delocalized -electrons, where n = 4).

The Use of Spectrophotometry UV-Vis for the Study of Porphyrins 91

It was recognized early that the intensity and colour of porphyrins are derived from the highly conjugated -electron systems and the most fascinating feature of porphyrins is their characteristic UV-visible spectra that consist of two distinct region regions: in the near

It has been well documented that changes in the conjugation pathway and symmetry of a porphyrin can affect its UV/Vis absorption spectrum (Gouterman, 1961; Whitten et al. 1968; Smith, 1976; Dolphin, 1978; Nappa & Valentine, 1978; Wang et al. 1984; Rubio et al. 1999).

The absorption spectrum of porphyrins has long been understood in terms of the highly

orbitals) model first applied in 1959 by Martin Gouterman that has discussed the importance of charge localization on electronic spectroscopic properties and has proposed the fourorbital model in the 1960s to explain the absorption spectra of porphyrins (Gouterman, 1959;

Fig. 6. UV-vis spectrum of porphyrin with in insert the enlargement of Q region between

250 350 450 550 650 750

**Wa ve le ng th (nm)**

energy state with less oscillator strength, giving rise to the Q-bands.

According to this theory, as reported in Figure 7, the absorption bands in porphyrin systems arise from transitions between two HOMOs and two LUMOs, and it is the identities of the metal center and the substituents on the ring that affect the relative energies of these transitions. The HOMOs were calculated to be an a1u and an a2u orbital, while the LUMOs were calculated to be a degenerate set of eg orbitals. Transitions between these orbitals gave rise to two excited states. Orbital mixing splits these two states in energy, creating a higher energy state with greater oscillator strength, giving rise to the Soret band, and a lower

The electronic absorption spectrum of a typical porphyrin (Fig. 6) consists therefore of two distinct regions. The first involve the transition from the ground state to the second excited state (S0 S2) and the corresponding band is called the Soret or B band. The range of

orbitals and two lowest unoccupied

\*

**3. Uv-vis spectra of porphyrins** 

ultraviolet and in the visible region (Fig. 6).

successful "four-orbital" (two highest occupied

Gouterman, 1961).

480-720 nm.

0

0,5

**Absorbance**

1

1,5

Fig. 4. Two-step one-flask room-temperature synthesis of porphyrins.

Its structure supports a highly stable configuration of single and double bonds with aromatic characteristics that permit the electrophilic substitution reactions typical of aromatic compounds such as halogenation, nitration, sulphonation, acylation, deuteration, formylation. Although this, in the porphyrins there are two different sites on the macrocycle where electrophylic substitution can take place with different reactivity (Milgrom, 1997): positions 5, 10, 15 e 20, called *meso* and positions 2, 3, 7, 8, 12, 13, 17 and 18, called -pyrrole positions (Fig. 5). The first kind of compounds are widely present in natural products, while the second have no counterpart in nature and were developed as functional artificial models. The activation of these sites depends of the porphyrins electronegativity that can be controlled by the choice of the metal to coordinate to the central nitrogen atoms. For this, the introduction of divalent central metals produces electronegative porphyrin ligands and these complexes can be substituted on their *meso*-carbon. On the other hand, metal ions in electrophylic oxidation states (e.g. Sn IV) tend to deactivate the *meso*-position and activate the pirrole to electrophylic attack. The chemical characteristics of substituents in -pyrrole and meso-position determine the water or solvent solubility of porphyrins.

Fig. 5. Porphyrin numeration.
