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β‐Tetrasubstituted meso ‐Tetra(4′‐ n ‐butylphenyl)porphyrins and Their Metal Complexes: Synthesis and Structural Properties
Author(s) -
Bhyrappa Puttaiah,
Sarangi Ujwal K.,
Velkannan Veerapandian,
Ramkumar Venkatachalam
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402661
Subject(s) - chemistry , porphyrin , crystal structure , electrochemistry , substituent , tetra , metal , redox , crystallography , absorption spectroscopy , pyrrole , stereochemistry , medicinal chemistry , inorganic chemistry , photochemistry , organic chemistry , electrode , physics , quantum mechanics
A new family of ‐tetrasubstituted porphyrins, 2,3,12,13‐tetra[phenylethynyl (PE)/4‐methoxyphenyl (4 ″ ‐CH 3 OPh)/4‐carboxy methylesterphenyl (4 ″ ‐CH 3 CO 2 Ph)]‐5,10,15,20‐tetrakis(4 ′ ‐ n ‐butylphenyl)porphyrin, H 2 T(4 ′ ‐BuPh)P(R) 4 and their metal (Co II , Cu II and Zn II ) complexes were synthesized using H 2 T(4 ′ ‐BuPh)PBr 4 as the precursor. These porphyrins show red‐shifted absorption bands and follow the nature of the β‐pyrrole substituent, R: PE > Br > 4 ″ ‐CO 2 CH 3 Ph ≈ 4 ″ ‐OCH 3 Ph. Crystal structures of MT(4 ′ ‐BuPh)P(PE) 4 (M = 2H, Co II , Cu II and Zn II ) derivatives were determined by single‐crystal XRD and they are isomorphous . The normal coordinate structure decomposition analysis of these structures reveal a slight wave ‐type of distortion of the macrocycle. Electrochemical redox properties of these derivatives show an anodic shift in potentials relative to their metallotetraphenylporphyrins (MTPPs), and this has been ascribed mainly to the electronic effect of the substituents.