Journal of the American Chemical Society p. 6616 - 6620 (1989)
Update date:2022-08-16
Topics:
Liou, Kwangkyoung
Jacobsen, Claus S.
Hoffman, Brian M.
Alloys of the isostructural porphyrinic molecular conductors (phthalocyaninato)cobalt iodide, Co(pc)I, and (phthalocyaninato)nickel iodide, Ni(pc)I, of composition CoxNi1-x(pc)I, x = 0.02, 0.10, 0.15, 0.20, 0.33, 0.50, 0.75, 0.90, and 0.95, have been prepared and shown to be homogeneous solid solutions by EPR and energy-dispersive X-ray microprobe analysis.The high (?RT ca. 500 Ω-1 cm-1) metallic conductivity of Ni(pc)I (x = 0) is associated with holes (positive thermopower) created by partial oxidation from the valence ?-band of the pc macrocycle,whereas the lower (?RT ca. 50 Ω-1 cm-1) nonmetallic conductivity of Co(pc)I (x = 1) is associated with electron carriers (negative thermopower) in the partially oxidized dz2 band of the metal-ion spine.For x a maximum appears in the conductivity between 170 and 260 K.This change is attributed to paramagnetic scattering by the Co(2+) local moments.With further increase in x the conductivity continues to change smoothly toward the nonmetallic behavior of Co(pc)I.Surprisingly, the thermopower does not smoothly tend toward the large negative values for Co(pc)I but becomes increasingly positive as x is increased from 0.2 to 0.75 and begins to decrease only by x ca. 0.90.These resultsare interpreted to mean that alloys with 0.2 View More
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