Solvent and Solvate Effects on the Cocrystallization of C₆₀with Co^II(OEP) or Zn^II(OEP) (OEP = Octaethylporphyrin)

Abstract

Variations in crystallization conditions produce dramatic changes in the composition and geometry of solvated porphyrin-fullerene cocrystals. The products obtained by cocrystallization from a benzene solution of C60 with a solution of MII(OEP) (M = Co or Zn) in a variety of solvents have been analyzed crystallographically. The cocrystals fall into three categories: Class 1, ordered crystals with a 1:1 porphyrin/fullerene ratio (CoII(OEP)·C60·CS2 (1), ZnII(OEP)­·C60·CS2 (2), CoII(OEP)­·C60·C4H8O2 (5), CoII(OEP)­·C60·1.5C6H6 (8); Class 2, ordered crystals with a 2:1 porphyrin/fullerene ratio (2ZnII(OEP)­·C60·0.75CCl4 (4) and 2CoII(OEP)­·C60·C4H8O (7)); and Class 3, crystals involving a five-coordinate metal and a disordered fullerene cage (ClCoIII(OEP)­·C60·CCl4 (3) and (C4H8O2)­ZnII(OEP)­·C60·C4H8O2 (6)). Class 1 crystals form in three different space groups, yet all contain two packing motifs: columns with significant porphyrin/porphyrin, fullerene/porphyrin, and fullerene/fullerene interactions and zigzag chains of fullerenes. Class 2 crystals are isostructural. Class 3 crystals vary due to differing axial ligands. Whether crystals with a 1:1 or 2:1 porphyrin/C60 ratio form depends upon the solvent rather than the amounts of components present in solution. Cocrystallization using ZnII(OEP) and chlorinated solvents appears as the preferred combination to produce ordered C60 molecules, and this situation may pertain for other fullerenes.

Favorite Orientation of the Carbon Cage and a Unique Two-Dimensional-Layered Packing Model in the Cocrystals of Nd@C82(I,II) Isomers with Decapyrrylcorannulene

“…Furthermore, in line with the geometrical parameters demonstrated in Figure S9 and Table S3, two of the three toluene molecules within 2DPC­{Nd@ C 2 v (9)-C 82 }·3C 7 H 8 and the two toluene molecules within 2DPC­{Nd@ C s (6)-C 82 }·2C 7 H 8 demonstrate C–H···π interactions with the C 2 v (9)-C 82 and C s (6)-C 82 cages, respectively. Therefore, the solvent toluene molecules have both π–π and C–H···π interactions, with the C 82 cages of Nd@C 82 (I,II) isomers in the crystallographic environment, similar to the interactions reported between solvent benzene molecules and C 60 in solvated crystals. , It is expected that such kinds of interactions would also influence the uneven charge distributions on the C cages of EMFs.…”

“…Recently, Balch et al investigated the effect of a solvent on the composition and structure of the cocrystal of C 60 with Co II (OEP) or Zn II (OEP). 20 Even though the crystallographic packing 2D-layered structure of 2DPC{Nd@C s (6)-C 82 }• 2C 7 H 8 is similar to that of 2DPC{Nd@C 2v (9)-C 82 }•3C 7 H 8 , the various number of solvent toluene molecules might bring about some important differences between the two structures. From Figure S10a, we can observe that within 2DPC{Nd@ C 2v (9)-C 82 }•3C 7 H 8 three toluene molecules face onto different pyramid C cages, with the nearest distances between the buckylball surface and toluene plane of 3.310(8), 3.300(8), and 3.373(9) Å.…”

“…Furthermore, in line with the geometrical parameters demonstrated in Figure S9 and Table S3, two of the three toluene molecules within 2DPC{Nd@C 2v (9) Nd@C 82 (I,II) isomers in the crystallographic environment, similar to the interactions reported between solvent benzene molecules and C 60 in solvated crystals. 20,21 It is expected that such kinds of interactions would also influence the uneven charge distributions on the C cages of EMFs.…”

“…Recently, Balch et al investigated the effect of a solvent on the composition and structure of the cocrystal of C 60 with Co II (OEP) or Zn II (OEP) . Even though the crystallographic packing 2D-layered structure of 2DPC­{Nd@ C s (6)-C 82 }·2C 7 H 8 is similar to that of 2DPC­{Nd@ C 2 v (9)-C 82 }·3C 7 H 8 , the various number of solvent toluene molecules might bring about some important differences between the two structures.…”

Rotation of fullerene molecules in the crystal lattice of fullerene/porphyrin: C60 and Sc3N@C80

“…Recently, the effect of the metal ion in the porphyrin and the role of the solvent in the crystallization of C 60 /MOEP (M=Co, Ni, Cu, and Zn) was thoroughly investigated. 18,19 However, the temperature driven fullerene molecule dynamics in the crystal lattice of co-crystals with MOEP are still unclear for this type of fullerene. The structure of the nitride clusterfullerene Sc 3 N@C 80 was reported more than two decades ago.…”