Effects of the central metal on stretching vibrational bands of the peripheral carbonyl moieties in formylated chlorophyll derivatives studied by Fourier-transform infrared spectroscopy

Abstract

The vibrational properties of metal complexes of monoformylated and diformylated chlorophyll derivatives were compared with those of the corresponding free-base chlorins to unravel the effects of the central metal on the carbonyl stretching vibration modes of the peripheral oxygen functional groups in the chlorin macrocycle by means of FTIR spectroscopy. The 3- C = O stretching vibrational bands of a 3-formyl group were shifted to lower wavenumbers by insertion of Zn and Cu into the center of the 3-formyl free-base chlorin. In contrast, the 7- and 8- C = O stretching vibrational bands of the formyl groups linked to the B-ring of the chlorin macrocycle were barely shifted even if 7- and 8-formyl free-base chlorins were metalated. The down-shifts of the 3- C = O and few shifts of the 7-/8- C = O vibrational stretching bands were in line with the results of DFT calculations. The difference in the effects of the central metal on the vibrational properties between the formyl group in the A-ring and those in the B-ring is ascribable to the different conjugation manners with the adjacent π-system: the 3-formyl group was connected to the chlorin 18π-system, whereas the 7-/8-formyl groups were conjugated to the rather isolated C 7– C 8 double bond. The 13- C = O stretching vibrational bands were shifted to lower wavenumbers by metalation. These down-shifts can also be rationalized by invoking the conjugation of the 13-keto group with the chlorin 18π-system.