Inorganic Chemistry, Vol.49, No.18, 8389-8400, 2010
Porphyrin-Fullerene, C-60, Cocrystallates: Influence of C-60 on the Porphyrin Ring Conformation
To examine the influence of fullerene on the macrocyclic ring conformation, crystal structures of a series of cocrystals of 2,3,5,10,12,13,15,20-octaphenylporphyrin, M(TPP)(Ph)(4) (M = 2H, Co(II), Cu(II)), and 2,312,13-tetramethyl-5,7,8,10,15,17,18,20-octaphenyl-porphinato copper(II), CuTPP(Ph)(4)(CH3)(4), derivatives with fullerene, C-60, were elucidated. Furthermore, crystal structures of the parent porphyrins, M(TPP)(Ph)(4) (M = Co(II), Cu(II)) complexes, were also determined. All the cocrystals revealed one-to-one stoichiometry between the porphyrin and C-60 and were free of lattice solvates. Porphyrin rings in M(TPP)(Ph)(4)center dot C-60 cocrystals revealed significant distortion with the root-mean-square (rms) value as high as 0.265(2) angstrom which is the average deviation of the 24 atoms core from the least-squares plane. Crystal structures of the parent M(TPP)(Ph)(4) (M = Co(II), Cu(II)) complexes indicated near planarity of the 24-atom core with the root-mean-square deviation value of 0.016(2)angstrom. Molecular packing in the M(TPP)(Ph)(4)center dot C-60 cocrystals showed essentially one-dimensional chains interconnected by weak interporphyrin and porphyrin fullerene close contacts. The N-porphyrin center dot center dot center dot C(C-60) shortest distances between the H-2(TPP)(Ph)(4) (M = 2H, Co(II), Cu(II)) and fullerene in the cocrystals are 3.031(5) angstrom, 3.062(4) angstrom, and 3.059(3) angstrom, respectively. Similarly, close contact M center dot center dot center dot C distances in the M(TPP)(Ph)4 center dot C-60 (M = Co(II), Cu(II)) are 2.761(6) angstrom and 2.886(3) angstrom, respectively. In the Cu(TPP)(Ph)(4)(CH3)(4)center dot C-60 cocrystal, the shift of macrocyclic ring toward planarity was evidenced from the rms value of 0.236(2) angstrom relative to that observed in CuTPP(Ph)(4)(CH3)(4)center dot CHCl3 (0.391(2) angstrom). The distortion of the macrocyclic ring in M(TPP)(Ph)(4)center dot C-60 complexes was examined by normal-coordinate-structure decomposition (NSD) analyses. Their out-of-plane displacement of the core atoms revealed predominant contribution being saddle (similar to 95-96%) and gentle domed distortions (3-4%). In the case of M(TPP)(Ph)4(CH3)(4)center dot C-60 cocrystal, it showed mainly saddled (similar to 83%), minimal ruffled (8%) and domed (8%) distortions of the macrocyclic ring. In-plane displacement on the 24-atom core of the porphyrin in these cocrystallates features generally a varying degree of N-sir (B-1g) and bre (A(1g)) distortions.