Crystal structures of meso-tetrakis(2′,6′/3′,5′-difluorophenyl)porphyrins and their metal complexes: Influence of position of the fluoro groups on their structural properties

• Published in: Journal of chemical sciences (Bangalore, India) India), 2016-04, Vol.128 (4), p.501-509
• Main Authors: PUTTAIAH, BHYRAPPA, KARUNANITHI, KARUPPAIAH
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry/Food Science
• ISSN: 0974-3626; 0973-7103
• DOI: 10.1007/s12039-016-1053-9

Two series of non-solvated structures of 5,10,15,20-tetrakis(2′,6′/3′,5′-difluorophenyl)porphyrins, H 2 T(2′,6′/3′,5′-DFP)P and their metal (Cu(II) and Zn(II)) complexes were determined by single crystal XRD. H 2 (2′,6′-DFP)P, 1 and its metal (Cu(II), 2 and Zn(II), 3 ) complexes showed near planar geometry of the porphyrin ring with the maximum root-mean-square (r.m.s.) which is the average deviation of the 24 core atoms from their least-squares plane by 0.056(3) Å while MT(3′,5′-DFP)P (Cu(II), 4 and Zn(II), 5 ) structures feature significant distortion of the macrocycle (r.m.s. = 0.22(2) Å). Nearly planar structures 1-3 revealed more number of intermolecular short contacts than that observed in nonplanar structures 4 and 5 . Normal coordinate structure decomposition analysis of the structures 1 - 3 revealed negligible wave distortion of the macrocycle but the corresponding nonplanar 4 and 5 structures feature mainly ruffled combined with minimal saddled distortions. The increased nonplanarity of the less sterically hindered derivatives 4 and 5 has been ascribed to intermolecular interactions and/or crystal packing forces. Graphical Abstract Two series of non-solvated 5,10,15,20-tetrakis(2′,6′/3′,5′-difluorophenyl)porphyrins, H2T(2′,6′/3′,5′-DFP)P and their (Cu(II) and Zn(II)) complexes have been examined by single crystal XRD and they showed near planarity of the macrocycle in the MT(2′,6′-DFP)Ps and enhanced nonplanar distortions in the MT(3′,5′-DFP)Ps structures.