Internal and external factors in the structural organization in cocrystals of the mixed-metal endohedrals (GdSc2N@Ih-C80, Gd2ScN@Ih-C80, and TbSc2N@Ih-C80) and nickel(II) octaethylporphyrin.
Structural characterizations of three new mixed-metal endohedrals, GdSc 2N@ I h -C80, Gd 2ScN@ I h -C80, and TbSc 2@ I h -C80, have been obtained by single-crystal X-ray diffraction on GdSc 2N@ I h -C80 x Ni (II)(OEP) x 2C 6H 6, Gd 2ScN@ I h -C 80 x Ni(II)(OEP) x 2C6H6, and TbSc 2N@ I h -C80 x Ni (II)(OEP) x 2C6H6. All three have I h -C 80 cages and planar MM' 2N units. The central nitride ion is positioned further from the larger Gd3+ or Tb3+ ions and closer to the smaller Sc3+ ions. The MM' 2N units show a remarkable degree of orientational order in these and related compounds in which the endohedral fullerene is cocrystallized with a metalloporphyrin. The MM' 2N units are oriented perpendicularly to the porphyrin plane and aligned along one of the N-Ni-N axes of the porphyrin. The smaller Sc3+ ions show a marked preference to lie near the porphyrin plane. The larger Gd3+ or Tb3+ ions assume positions further from the plane of the porphyrin. The roles of dipole forces and electrostatic forces in ordering these cocrystals of endohedral fullerenes and metalloporphyrins are considered.
Stevenson
Steven
S
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, USA.
Chancellor
Christopher J
CJ
Lee
Hon Man
HM
Olmstead
Marilyn M
MM
Balch
Alan L
AL
D003460:Crystallization; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D011166:Porphyrins / Q000737:chemistry*
D008670:Metals; D011166:Porphyrins