Internal And External Factors in the Structural Organization in Cocrystals of the Mixed-Metal Endohedrals (GdSc2N@I(H)-C(80), Gd(2)ScN@I(H)-C(80), And TbSc(2)N@I(H)C(80) ) And Nickel(II) Octaethylporphyrin
Structural characterizations of three new mixed-metal endohedrals, GdSc{sub 2}N@I{sub h}-C{sub 80}, Gd{sub 2}ScN@I{sub h}-C{sub 80}, and TbSc{sub 2}@I{sub h}-C{sub 80}, have been obtained by single-crystal X-ray diffraction on GdSc{sub 2}N@I{sub h}-C{sub 80}{center_dot}Ni{sup II}(OEP){center_dot}2C{sub 6}H{sub 6}, Gd{sub 2}ScN@I{sub h}-C{sub 80}{center_dot}Ni{sup II}(OEP){center_dot}2C{sub 6}H{sub 6}, and TbSc{sub 2}N@I{sub h}-C{sub 80}{center_dot}Ni{sup II}(OEP){center_dot}2C{sub 6}H{sub 6}. All three have I{sub h}-C{sub 80} cages and planar MM'{sub 2}N units. The central nitride ion is positioned further from the larger Gd{sup 3+} or Tb{sup 3+} ions and closer to the smaller Sc{sup 3+} ions. The MM'{sub 2}N 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'{sub 2}N units are oriented perpendicularly to the porphyrin plane and aligned along one of the N-Ni-N axes of the porphyrin. The smaller Sc{sup 3+} ions show a marked preference to lie near the porphyrin plane. The larger Gd{sup 3+} or Tb{sup 3+} 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.
- Research Organization:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC02-76SF00515
- OSTI ID:
- 953574
- Report Number(s):
- SLAC-REPRINT-2009-310; INOCAJ; TRN: US201002%%1402
- Journal Information:
- Inorg. Chem 47:1420,2008, Vol. 47, Issue 5; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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