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Title: Cu(pc)I: a molecular metal with a one-dimensional array of local moments embedded in a Fermi Sea of charge carriers

Abstract

Treatment of (phthalocyaninato)copper(II), Cu(pc), with elemental iodine affords (phthalocyaninato)copper iodide, Cu(pc)I. This material is comprised of metal-over-metal stacks of partially oxidized Cu(pc) groups surrounded by linear chains of I/sub 3//sup -/ ions. Reflectivity spectra from single crystals of Cu(pc)I exhibit a very sharp plasma edge for light polarized parallel to the stacking direction and four-probe conductivity measurements show a room temperature conductivity of ca. 10/sup 3/ Omega/sup -1/ cm/sup -1/ along this direction. Together these measurements indicate that Cu(pc)I is the most highly conductive porphyrinic molecular metal studied to date and is among the most conductive molecular crystals known. Crystal data: tetragonal, space group D/sub 4h//sup 2/-P4/mcc with a = 13.888 (12) A, c = 6.390 (8) A, V = 1232 A/sup 3/, and Z = 2. Thermoelectric power and magnetic susceptibility measurements show that the charge carriers of Cu(pc)I are holes in the 5/6 filled band comprised of overlapping p-..pi.. orbitals from adjacent pc rings. The metal sites in this material retain their paramagnetic Cu/sup 2 +/ oxidation state, and thus Cu(pc)I represents the first example of a one-dimensional array of local moments embedded in a Fermi sea of charge carriers.

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL
OSTI Identifier:
6813122
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 109:4
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COPPER COMPLEXES; CRYSTAL STRUCTURE; ELECTRIC CONDUCTIVITY; MAGNETIC SUSCEPTIBILITY; REFLECTIVITY; THERMOELECTRIC PROPERTIES; ORGANIC IODINE COMPOUNDS; PHTHALOCYANINES; ELECTRON SPIN RESONANCE; EXPERIMENTAL DATA; LATTICE PARAMETERS; MONOCRYSTALS; SPACE GROUPS; COMPLEXES; CRYSTALS; DATA; DYES; ELECTRICAL PROPERTIES; HETEROCYCLIC COMPOUNDS; INFORMATION; MAGNETIC PROPERTIES; MAGNETIC RESONANCE; NUMERICAL DATA; OPTICAL PROPERTIES; ORGANIC COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; PHYSICAL PROPERTIES; RESONANCE; SURFACE PROPERTIES; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Ogawa, M Y, Martinsen, J, Palmer, S M, Stanton, J L, Tanaka, J, Greene, R L, Hoffman, B M, and Ibers, J A. Cu(pc)I: a molecular metal with a one-dimensional array of local moments embedded in a Fermi Sea of charge carriers. United States: N. p., 1987. Web. doi:10.1021/ja00238a021.
Ogawa, M Y, Martinsen, J, Palmer, S M, Stanton, J L, Tanaka, J, Greene, R L, Hoffman, B M, & Ibers, J A. Cu(pc)I: a molecular metal with a one-dimensional array of local moments embedded in a Fermi Sea of charge carriers. United States. https://doi.org/10.1021/ja00238a021
Ogawa, M Y, Martinsen, J, Palmer, S M, Stanton, J L, Tanaka, J, Greene, R L, Hoffman, B M, and Ibers, J A. 1987. "Cu(pc)I: a molecular metal with a one-dimensional array of local moments embedded in a Fermi Sea of charge carriers". United States. https://doi.org/10.1021/ja00238a021.
@article{osti_6813122,
title = {Cu(pc)I: a molecular metal with a one-dimensional array of local moments embedded in a Fermi Sea of charge carriers},
author = {Ogawa, M Y and Martinsen, J and Palmer, S M and Stanton, J L and Tanaka, J and Greene, R L and Hoffman, B M and Ibers, J A},
abstractNote = {Treatment of (phthalocyaninato)copper(II), Cu(pc), with elemental iodine affords (phthalocyaninato)copper iodide, Cu(pc)I. This material is comprised of metal-over-metal stacks of partially oxidized Cu(pc) groups surrounded by linear chains of I/sub 3//sup -/ ions. Reflectivity spectra from single crystals of Cu(pc)I exhibit a very sharp plasma edge for light polarized parallel to the stacking direction and four-probe conductivity measurements show a room temperature conductivity of ca. 10/sup 3/ Omega/sup -1/ cm/sup -1/ along this direction. Together these measurements indicate that Cu(pc)I is the most highly conductive porphyrinic molecular metal studied to date and is among the most conductive molecular crystals known. Crystal data: tetragonal, space group D/sub 4h//sup 2/-P4/mcc with a = 13.888 (12) A, c = 6.390 (8) A, V = 1232 A/sup 3/, and Z = 2. Thermoelectric power and magnetic susceptibility measurements show that the charge carriers of Cu(pc)I are holes in the 5/6 filled band comprised of overlapping p-..pi.. orbitals from adjacent pc rings. The metal sites in this material retain their paramagnetic Cu/sup 2 +/ oxidation state, and thus Cu(pc)I represents the first example of a one-dimensional array of local moments embedded in a Fermi sea of charge carriers.},
doi = {10.1021/ja00238a021},
url = {https://www.osti.gov/biblio/6813122}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 109:4,
place = {United States},
year = {Wed Feb 18 00:00:00 EST 1987},
month = {Wed Feb 18 00:00:00 EST 1987}
}