Porphyrin amino acids-amide coupling, redox and photophysical properties of bis(porphyrin) amides

Abstract

New trans-AB 2 C meso-substituted porphyrin amino acid esters with meso-substituents of tunable electron withdrawing power (B = mesityl, 4-C 6 H 4 F, 4-C 6 H 4 CF 3, C 6 F 5) were prepared as free amines 3a-3d, as N-acetylated derivatives Ac-3a-Ac-3d and corresponding zinc(ii) complexes Zn-Ac-3a-Zn-Ac-3d. Several amide-linked bis(porphyrins) with a tunable electron density at each porphyrin site were obtained from the amino porphyrin precursors by condensation reactions (4a-4d) and mono- and bis(zinc(ii)) complexes Zn 2 -4d and Zn 1 Zn 2 -4d were prepared. The electronic interaction between individual porphyrin units in bis(porphyrins) 4 is probed by electrochemical experiments (CV, EPR), electronic absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy in combination with DFT/PCM calculations on diamagnetic neutral bis(porphyrins) 4 and on respective charged mixed-valent radicals 4 +/-. The interaction via the -C 6 H 4 -NHCO-C 6 H 4 - bridge, the site of oxidation and reduction and the lowest excited singlet state S 1, is tuned by the substituents on the individual porphyrins and the metalation state. © The Royal Society of Chemistry 2013.