Electrically conductive metallomacrocyclic assemblies. High-resolution solid-state NMR spectroscopy as a probe of local architecture and electronic structure in phthalocyanine molecular and macromolecular "metals"

Paul J. Toscano, Tobin J Marks

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Abstract

This contribution reports a high-resolution solid-state 13C CPMAS study of the low-dimensional phthalocyanine (Pc) conductors Ni(Pc)I, H2(Pc)I, {[Si(Pc)O]I1.1}n, ([Si(Pc)O]Xy}n (X = BF4, PF6, SbF6, γ ∼0.35), {[Ge(Pc)]I1.1)n, and Ni(Pc)Xz (X = BF4, PF6, SbF6, z ≈ 0.33), as well as of the precursors Ni(Pc), H2(Pc), [Si(Pc)O]n, and [Ge(Pc)O]n. For the partially oxidized materials, large, locally resolved 13C-conduction electron Knight shifts with dispersions as large as 400 ppm and multiplicities in accord with crystallographic site symmetries are observed. By using Ni(Pc)I selectively labeled with 13C at the 1,1′ skeletal positions and with 2H at the 4,4′ hydrogen atom positions, along with dipole dephasing techniques, it is possible to completely and unambiguously assign the CPMAS spectrum. From this information is obtained a map of the conduction electron hyperfine interaction about the carbon framework of the macrocycle. In Ni(Pc)I, the ratios of the 1,1′ to the 2,2′ 13C spin-lattice relaxation times conform approximately to the Korringa relationship at room temperature. For the partially oxidized phthalocyanine series as a whole, a linear relationship is observed between the individual 1,1′ and 2,2′ 13C Knight shifts and the corresponding Pauli-like magnetic susceptibilities.

Original languageEnglish
Pages (from-to)437-444
Number of pages8
JournalJournal of the American Chemical Society
Volume108
Issue number3
Publication statusPublished - 1986

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Nuclear magnetic resonance spectroscopy
Electronic structure
Magnetic Resonance Spectroscopy
Metals
Spin-lattice relaxation
Electrons
Magnetic susceptibility
Dispersions
Relaxation time
Atoms
Hydrogen
Carbon
Temperature
phthalocyanine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Electrically conductive metallomacrocyclic assemblies. High-resolution solid-state NMR spectroscopy as a probe of local architecture and electronic structure in phthalocyanine molecular and macromolecular {"}metals{"}",
abstract = "This contribution reports a high-resolution solid-state 13C CPMAS study of the low-dimensional phthalocyanine (Pc) conductors Ni(Pc)I, H2(Pc)I, {[Si(Pc)O]I1.1}n, ([Si(Pc)O]Xy}n (X = BF4, PF6, SbF6, γ ∼0.35), {[Ge(Pc)]I1.1)n, and Ni(Pc)Xz (X = BF4, PF6, SbF6, z ≈ 0.33), as well as of the precursors Ni(Pc), H2(Pc), [Si(Pc)O]n, and [Ge(Pc)O]n. For the partially oxidized materials, large, locally resolved 13C-conduction electron Knight shifts with dispersions as large as 400 ppm and multiplicities in accord with crystallographic site symmetries are observed. By using Ni(Pc)I selectively labeled with 13C at the 1,1′ skeletal positions and with 2H at the 4,4′ hydrogen atom positions, along with dipole dephasing techniques, it is possible to completely and unambiguously assign the CPMAS spectrum. From this information is obtained a map of the conduction electron hyperfine interaction about the carbon framework of the macrocycle. In Ni(Pc)I, the ratios of the 1,1′ to the 2,2′ 13C spin-lattice relaxation times conform approximately to the Korringa relationship at room temperature. For the partially oxidized phthalocyanine series as a whole, a linear relationship is observed between the individual 1,1′ and 2,2′ 13C Knight shifts and the corresponding Pauli-like magnetic susceptibilities.",
author = "Toscano, {Paul J.} and Marks, {Tobin J}",
year = "1986",
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volume = "108",
pages = "437--444",
journal = "Journal of the American Chemical Society",
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T1 - Electrically conductive metallomacrocyclic assemblies. High-resolution solid-state NMR spectroscopy as a probe of local architecture and electronic structure in phthalocyanine molecular and macromolecular "metals"

AU - Toscano, Paul J.

AU - Marks, Tobin J

PY - 1986

Y1 - 1986

N2 - This contribution reports a high-resolution solid-state 13C CPMAS study of the low-dimensional phthalocyanine (Pc) conductors Ni(Pc)I, H2(Pc)I, {[Si(Pc)O]I1.1}n, ([Si(Pc)O]Xy}n (X = BF4, PF6, SbF6, γ ∼0.35), {[Ge(Pc)]I1.1)n, and Ni(Pc)Xz (X = BF4, PF6, SbF6, z ≈ 0.33), as well as of the precursors Ni(Pc), H2(Pc), [Si(Pc)O]n, and [Ge(Pc)O]n. For the partially oxidized materials, large, locally resolved 13C-conduction electron Knight shifts with dispersions as large as 400 ppm and multiplicities in accord with crystallographic site symmetries are observed. By using Ni(Pc)I selectively labeled with 13C at the 1,1′ skeletal positions and with 2H at the 4,4′ hydrogen atom positions, along with dipole dephasing techniques, it is possible to completely and unambiguously assign the CPMAS spectrum. From this information is obtained a map of the conduction electron hyperfine interaction about the carbon framework of the macrocycle. In Ni(Pc)I, the ratios of the 1,1′ to the 2,2′ 13C spin-lattice relaxation times conform approximately to the Korringa relationship at room temperature. For the partially oxidized phthalocyanine series as a whole, a linear relationship is observed between the individual 1,1′ and 2,2′ 13C Knight shifts and the corresponding Pauli-like magnetic susceptibilities.

AB - This contribution reports a high-resolution solid-state 13C CPMAS study of the low-dimensional phthalocyanine (Pc) conductors Ni(Pc)I, H2(Pc)I, {[Si(Pc)O]I1.1}n, ([Si(Pc)O]Xy}n (X = BF4, PF6, SbF6, γ ∼0.35), {[Ge(Pc)]I1.1)n, and Ni(Pc)Xz (X = BF4, PF6, SbF6, z ≈ 0.33), as well as of the precursors Ni(Pc), H2(Pc), [Si(Pc)O]n, and [Ge(Pc)O]n. For the partially oxidized materials, large, locally resolved 13C-conduction electron Knight shifts with dispersions as large as 400 ppm and multiplicities in accord with crystallographic site symmetries are observed. By using Ni(Pc)I selectively labeled with 13C at the 1,1′ skeletal positions and with 2H at the 4,4′ hydrogen atom positions, along with dipole dephasing techniques, it is possible to completely and unambiguously assign the CPMAS spectrum. From this information is obtained a map of the conduction electron hyperfine interaction about the carbon framework of the macrocycle. In Ni(Pc)I, the ratios of the 1,1′ to the 2,2′ 13C spin-lattice relaxation times conform approximately to the Korringa relationship at room temperature. For the partially oxidized phthalocyanine series as a whole, a linear relationship is observed between the individual 1,1′ and 2,2′ 13C Knight shifts and the corresponding Pauli-like magnetic susceptibilities.

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