Structural and photophysical studies of trans-AB(2)C-substituted porphyrin ligands and their zinc and copper complexes |
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Authors: | Heinze Katja Reinhart Anja |
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Institution: | Department of Inorganic Chemistry, University of Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany. katja.heinze@urz.uni-heidelberg.de |
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Abstract: | trans-AB(2)C porphyrins with A = C(6)H(4)-COOR, C = C(6)H(4)-NX(2) and B = C(6)H(5) (R = CH(3), H; X = O, H) have been synthesised by a rational high-yield procedure (1a-1d) and their zinc(ii) and copper(ii) complexes have been prepared (2a-2d, 3a-3d ).1a, 2a .THF and 3a display different distortions of the porphyrin core as shown by single crystal X-ray crystallography and NSD analyses. The Soret and Q bands of free-base and metalated porphyrins with mixed electron donating and withdrawing substituents (NH(2)/COOR) are red-shifted as are the corresponding emission bands of free-base and zinc porphyrins. The electronic asymmetry revealed by spectrocopy is rationalised by DFT calculations. |
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