TY - JOUR
T1 - Unusual band-filling and counterion ordering effects in a phthalocyanine molecular metal. Single crystal studies of Ni(Pc) (C104)y
AU - Almeida, M.
AU - Kanatzidis, Mercouri G
AU - Tonge, L. M.
AU - Marks, Tobin J
AU - Marcy, H. O.
AU - McCarthy, W. J.
AU - Kannewurf, C. R.
PY - 1987
Y1 - 1987
N2 - The phthalocyanine molecular metal Ni(Pc) (C104)y, y=0.39-0.47 for most crystals, has been synthesized by electrocrystallization techniques. The structure of a crystal with y=0.42 consists of staggered (39.5°) Ni(Pc)+0.42 units stacked at 3.233(1) Å separations and disordered, off-axis C10-
4 ions. At lower temperatures, the C10-
4 ions undergo a transition to an ordered arrangement. At 300°K, σ{norm of matrix}=700±200Ω-1 cm-1 with metal-like (dσ/dT4 ordering rather than macroscopic fracturing. Thermoelectric power data are also metal-like (S≈T) with no evidence of the aforementioned discontinuities. Room temperature values of S=20-35 μVK-1 are in accord with the relatively high degree of Ni(Pc)+ρ partial oxidation. Polarized single crystal reflectance data reveal a plasma edge, the high energy of which is also explicable in terms of the relatively high degree of partial oxidation. Analysis of the thermoelectric power and optical data yields, in both cases, a tight-binding bandwidth of ca. 1.5 eV.
AB - The phthalocyanine molecular metal Ni(Pc) (C104)y, y=0.39-0.47 for most crystals, has been synthesized by electrocrystallization techniques. The structure of a crystal with y=0.42 consists of staggered (39.5°) Ni(Pc)+0.42 units stacked at 3.233(1) Å separations and disordered, off-axis C10-
4 ions. At lower temperatures, the C10-
4 ions undergo a transition to an ordered arrangement. At 300°K, σ{norm of matrix}=700±200Ω-1 cm-1 with metal-like (dσ/dT4 ordering rather than macroscopic fracturing. Thermoelectric power data are also metal-like (S≈T) with no evidence of the aforementioned discontinuities. Room temperature values of S=20-35 μVK-1 are in accord with the relatively high degree of Ni(Pc)+ρ partial oxidation. Polarized single crystal reflectance data reveal a plasma edge, the high energy of which is also explicable in terms of the relatively high degree of partial oxidation. Analysis of the thermoelectric power and optical data yields, in both cases, a tight-binding bandwidth of ca. 1.5 eV.
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U2 - 10.1016/0038-1098(87)90270-5
DO - 10.1016/0038-1098(87)90270-5
M3 - Article
AN - SCOPUS:0023397431
VL - 63
SP - 457
EP - 461
JO - Solid State Communications
JF - Solid State Communications
SN - 0038-1098
IS - 6
ER -