Cofacial assembly of partially oxidized metallomacrocycles as an approach to controlling lattice architecture in low-dimensional molecular solids. Synthesis and properties of cofacially joined silicon and germanium hemiporphyrazine polymers

Carl W. Dirk, Tobin J Marks

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Abstract

This contribution reports an integrated chemical, spectroscopic, X-ray diffractometric, and charge transport investigation of the cofacially linked metallomacrocyclic polymers [M(hp)O]n, where M = Si and Ge and hp = hemiporphyrazinato. The synthesis of the new M = Si compound (from Si(hp)Cl2 and Si(hp)(OH)2) and modified syntheses of the M = Ge analogue are reported. Optical spectra are discussed as a function of M and X for the various M(hp)X2 derivatives. Radiotracer studies of the degree of polymerization using M(hp)(O3H)2 precursors yield n values for typical [M(hp)O]n samples of 20 (M = Si) and 50 (M = Ge). On the basis of data for monomeric M(hp)X2 derivatives, both vibrational and high-resolution solid-state 13C NMR spectra of the [M(hp)O]n polymers can be assigned in terms of a cofacially linked polymer architecture. X-ray diffraction data suggest that the [M(hp)O]n polymers are crystalline and structurally similar; however, the crystal structures are not similar to that of [Fe(hp)O]n nor to those of the analogous [M(Pc)O]n polymers, Pc = phthalocyaninato. Doping of the [M(hp)O]n polymers with iodine using several procedures results in iodine uptake but no significant increase in electrical conductivity. It appears that iodination is accompanied by destruction of the polymer M-O-M framework.

Original languageEnglish
Pages (from-to)4325-4332
Number of pages8
JournalInorganic Chemistry
Volume23
Issue number25
Publication statusPublished - 1984

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Germanium
Silicon
germanium
Polymers
assembly
polymers
silicon
synthesis
Iodine
iodine
Derivatives
destruction
optical spectrum
Charge transfer
x rays
polymerization
Crystal structure
Polymerization
Doping (additives)
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Cofacial assembly of partially oxidized metallomacrocycles as an approach to controlling lattice architecture in low-dimensional molecular solids. Synthesis and properties of cofacially joined silicon and germanium hemiporphyrazine polymers",
abstract = "This contribution reports an integrated chemical, spectroscopic, X-ray diffractometric, and charge transport investigation of the cofacially linked metallomacrocyclic polymers [M(hp)O]n, where M = Si and Ge and hp = hemiporphyrazinato. The synthesis of the new M = Si compound (from Si(hp)Cl2 and Si(hp)(OH)2) and modified syntheses of the M = Ge analogue are reported. Optical spectra are discussed as a function of M and X for the various M(hp)X2 derivatives. Radiotracer studies of the degree of polymerization using M(hp)(O3H)2 precursors yield n values for typical [M(hp)O]n samples of 20 (M = Si) and 50 (M = Ge). On the basis of data for monomeric M(hp)X2 derivatives, both vibrational and high-resolution solid-state 13C NMR spectra of the [M(hp)O]n polymers can be assigned in terms of a cofacially linked polymer architecture. X-ray diffraction data suggest that the [M(hp)O]n polymers are crystalline and structurally similar; however, the crystal structures are not similar to that of [Fe(hp)O]n nor to those of the analogous [M(Pc)O]n polymers, Pc = phthalocyaninato. Doping of the [M(hp)O]n polymers with iodine using several procedures results in iodine uptake but no significant increase in electrical conductivity. It appears that iodination is accompanied by destruction of the polymer M-O-M framework.",
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T1 - Cofacial assembly of partially oxidized metallomacrocycles as an approach to controlling lattice architecture in low-dimensional molecular solids. Synthesis and properties of cofacially joined silicon and germanium hemiporphyrazine polymers

AU - Dirk, Carl W.

AU - Marks, Tobin J

PY - 1984

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N2 - This contribution reports an integrated chemical, spectroscopic, X-ray diffractometric, and charge transport investigation of the cofacially linked metallomacrocyclic polymers [M(hp)O]n, where M = Si and Ge and hp = hemiporphyrazinato. The synthesis of the new M = Si compound (from Si(hp)Cl2 and Si(hp)(OH)2) and modified syntheses of the M = Ge analogue are reported. Optical spectra are discussed as a function of M and X for the various M(hp)X2 derivatives. Radiotracer studies of the degree of polymerization using M(hp)(O3H)2 precursors yield n values for typical [M(hp)O]n samples of 20 (M = Si) and 50 (M = Ge). On the basis of data for monomeric M(hp)X2 derivatives, both vibrational and high-resolution solid-state 13C NMR spectra of the [M(hp)O]n polymers can be assigned in terms of a cofacially linked polymer architecture. X-ray diffraction data suggest that the [M(hp)O]n polymers are crystalline and structurally similar; however, the crystal structures are not similar to that of [Fe(hp)O]n nor to those of the analogous [M(Pc)O]n polymers, Pc = phthalocyaninato. Doping of the [M(hp)O]n polymers with iodine using several procedures results in iodine uptake but no significant increase in electrical conductivity. It appears that iodination is accompanied by destruction of the polymer M-O-M framework.

AB - This contribution reports an integrated chemical, spectroscopic, X-ray diffractometric, and charge transport investigation of the cofacially linked metallomacrocyclic polymers [M(hp)O]n, where M = Si and Ge and hp = hemiporphyrazinato. The synthesis of the new M = Si compound (from Si(hp)Cl2 and Si(hp)(OH)2) and modified syntheses of the M = Ge analogue are reported. Optical spectra are discussed as a function of M and X for the various M(hp)X2 derivatives. Radiotracer studies of the degree of polymerization using M(hp)(O3H)2 precursors yield n values for typical [M(hp)O]n samples of 20 (M = Si) and 50 (M = Ge). On the basis of data for monomeric M(hp)X2 derivatives, both vibrational and high-resolution solid-state 13C NMR spectra of the [M(hp)O]n polymers can be assigned in terms of a cofacially linked polymer architecture. X-ray diffraction data suggest that the [M(hp)O]n polymers are crystalline and structurally similar; however, the crystal structures are not similar to that of [Fe(hp)O]n nor to those of the analogous [M(Pc)O]n polymers, Pc = phthalocyaninato. Doping of the [M(hp)O]n polymers with iodine using several procedures results in iodine uptake but no significant increase in electrical conductivity. It appears that iodination is accompanied by destruction of the polymer M-O-M framework.

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