title: Structural and photophysical studies of trans-AB(2)C-substituted porphyrin ligands and their zinc and copper complexes.
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.
authors.affiliation: Department of Inorganic Chemistry, University of Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany. katja.heinze@urz.uni-heidelberg.de
authors.forename: Katja
authors.initials: K
authors.lastname: Heinze
authors.forename: Anja
authors.initials: A
authors.lastname: Reinhart
mesh_terms: D002152:Calorimetry, Differential Scanning; D003300:Copper / Q000737:chemistry*; D004563:Electrochemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010455:Peptides / Q000737:chemistry; D010777:Photochemistry; D011166:Porphyrins / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D015032:Zinc / Q000737:chemistry*
chemical_list: D008024:Ligands; D010455:Peptides; D011166:Porphyrins; D003300:Copper; D015032:Zinc