Cofacial assembly of partially oxidized metallomacrocycles as an approach to controlling lattice architecture in low-dimensional molecular "metals". Probing band structure-counterion interactions in conductive [M(phthalocyaninato)O]n macromolecules using nitrosonium oxidants

Tamotsu Inabe, John G. Gaudiello, Michael K. Moguel, Tobin J Marks, Robert L. Burton, William J. McCarthy, Carl R. Kannewurf, Tobin J. Marks

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Abstract

This contribution reports an integrated chemical and physicochemical investigation of the consequences of doping the cofacially joined metallomacrocyclic polymers [M(Pc)O]n, M = Si and Ge, with the nitrosonium salts NO+X-, X- = BF4-, PF6-, and SbF6-. In the case of [Si(Pc)O]n, doped products {[Si(Pc)O]Xy}n are obtained with a limiting stoichiometry y ≃ 0.36 (essentially identical with band-fillings obtained with halogen oxidants). In contrast, NO+X- doping results in decomposition of [Ge(Pc)O]n. Upon incremental NO+X- doping of [Si(Pc)O]n, transmission infrared spectra reveal the progressive growth of electronic absorption, and transmission optical spectra reveal the formation of Pc π radical cation species. Studies of the NO+X- doping process by X-ray diffractometry suggest that it is largely inhomogeneous. Computer-assisted analysis of the {[Si(Pc)O]Xy}n powder diffraction data (aided by judiciously chosen model compounds) indicates crystal structures closely analogous to those of {[Si(Pc)O](I3)0.37}n, {[Si(Pc)O](Br3)0.37}n, Ni(Pc)(ClO4)0.40, and Ni(Pc)(BF4)0.35. The data can be indexed in the tetragonal space group P4/mcc, Z = 2, with a = 13.70 (7) Å, c = 6.58 (4) Å, phthalocyanine staggering angle = 40 (2)° (X- = BF4-); a = 13.98 (6) Å, c = 6.58 (4) Å; phthalocyanine staggering angle = 40 (2)° (X- = PF6-); a = 14.31 (4) Å, c = 6.58 (4) Å, phthalocyanine staggering angle = 40 (2)° (X̊ = SbF6-). It appears that the X- ions are disordered along c. ESR spectra reveal nearly free electron g values, in accord with the ligand-centered π radical character of the oxidation. As a consequence of the pronounced unidimensionality and minimal interaction of the carriers with heavy atoms, X-band powder ESR line widths are rather narrow (2.9-0.36 G) and decrease in the order I3- > SbF6- > PF6- > BF4-. For {[Si(Pc)O](BF4)0.36}n, the line width is virtually temperature-independent from 4 to 300 K. Variable temperature (4-300 K) static magnetic susceptibility studies of the {[Si(Pc)O]Xy}n materials reveal a small, sample-dependent Curie-like component and a Pauli-like, weakly temperature dependent contribution. Within experimental error, the Pauli-like susceptibility is independent of X-. Optical reflectivity studies of these materials reveal a plasma edge in the infrared. A Drude analysis of the data yields plasma frequency and tight-binding bandwidth parameters which are essentially independent of X-. Four-probe electrical conductivity studies of polycrystalline {[Si(Pc)O]Xy}n samples reveal a sharp increase of conductivity with increasing y. The temperature dependence of the data can be most convincingly fit to a transport model involving fluctuation-induced carrier tunneling through parabolic potential barriers that separate the high conductivity regions. As for the other collective properties, the charge transport properties are relatively insensitive to X-. A thermochemical analysis (Born-Haber cycle) indicates that the energetics of [Si(Pc)O]n doping with Br2, I2, and NO+X- are surprisingly similar. The small magnitude of the band structure-counterion interactions in the {[Si(Pc)O]Xy}n materials is attributed both to the local electronic and molecular structure of the phthalocyanine subunits as well as the overall stacking rigidity imposed by the -(Si-O-)n chains.

Original languageEnglish
Pages (from-to)7595-7608
Number of pages14
JournalJournal of the American Chemical Society
Volume108
Issue number24
Publication statusPublished - 1986

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Macromolecules
Oxidants
Band structure
Metals
Doping (additives)
Temperature
Linewidth
Paramagnetic resonance
Powder Diffraction
Electric Conductivity
Halogens
Plasmas
Molecular Structure
Infrared transmission
Powders
Cations
Light transmission
Polymers
Magnetic susceptibility
Salts

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Cofacial assembly of partially oxidized metallomacrocycles as an approach to controlling lattice architecture in low-dimensional molecular "metals". Probing band structure-counterion interactions in conductive [M(phthalocyaninato)O]n macromolecules using nitrosonium oxidants. / Inabe, Tamotsu; Gaudiello, John G.; Moguel, Michael K.; Marks, Tobin J; Burton, Robert L.; McCarthy, William J.; Kannewurf, Carl R.; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 108, No. 24, 1986, p. 7595-7608.

Research output: Contribution to journalArticle

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title = "Cofacial assembly of partially oxidized metallomacrocycles as an approach to controlling lattice architecture in low-dimensional molecular {"}metals{"}. Probing band structure-counterion interactions in conductive [M(phthalocyaninato)O]n macromolecules using nitrosonium oxidants",
abstract = "This contribution reports an integrated chemical and physicochemical investigation of the consequences of doping the cofacially joined metallomacrocyclic polymers [M(Pc)O]n, M = Si and Ge, with the nitrosonium salts NO+X-, X- = BF4-, PF6-, and SbF6-. In the case of [Si(Pc)O]n, doped products {[Si(Pc)O]Xy}n are obtained with a limiting stoichiometry y ≃ 0.36 (essentially identical with band-fillings obtained with halogen oxidants). In contrast, NO+X- doping results in decomposition of [Ge(Pc)O]n. Upon incremental NO+X- doping of [Si(Pc)O]n, transmission infrared spectra reveal the progressive growth of electronic absorption, and transmission optical spectra reveal the formation of Pc π radical cation species. Studies of the NO+X- doping process by X-ray diffractometry suggest that it is largely inhomogeneous. Computer-assisted analysis of the {[Si(Pc)O]Xy}n powder diffraction data (aided by judiciously chosen model compounds) indicates crystal structures closely analogous to those of {[Si(Pc)O](I3)0.37}n, {[Si(Pc)O](Br3)0.37}n, Ni(Pc)(ClO4)0.40, and Ni(Pc)(BF4)0.35. The data can be indexed in the tetragonal space group P4/mcc, Z = 2, with a = 13.70 (7) {\AA}, c = 6.58 (4) {\AA}, phthalocyanine staggering angle = 40 (2)° (X- = BF4-); a = 13.98 (6) {\AA}, c = 6.58 (4) {\AA}; phthalocyanine staggering angle = 40 (2)° (X- = PF6-); a = 14.31 (4) {\AA}, c = 6.58 (4) {\AA}, phthalocyanine staggering angle = 40 (2)° (X̊ = SbF6-). It appears that the X- ions are disordered along c. ESR spectra reveal nearly free electron g values, in accord with the ligand-centered π radical character of the oxidation. As a consequence of the pronounced unidimensionality and minimal interaction of the carriers with heavy atoms, X-band powder ESR line widths are rather narrow (2.9-0.36 G) and decrease in the order I3- > SbF6- > PF6- > BF4-. For {[Si(Pc)O](BF4)0.36}n, the line width is virtually temperature-independent from 4 to 300 K. Variable temperature (4-300 K) static magnetic susceptibility studies of the {[Si(Pc)O]Xy}n materials reveal a small, sample-dependent Curie-like component and a Pauli-like, weakly temperature dependent contribution. Within experimental error, the Pauli-like susceptibility is independent of X-. Optical reflectivity studies of these materials reveal a plasma edge in the infrared. A Drude analysis of the data yields plasma frequency and tight-binding bandwidth parameters which are essentially independent of X-. Four-probe electrical conductivity studies of polycrystalline {[Si(Pc)O]Xy}n samples reveal a sharp increase of conductivity with increasing y. The temperature dependence of the data can be most convincingly fit to a transport model involving fluctuation-induced carrier tunneling through parabolic potential barriers that separate the high conductivity regions. As for the other collective properties, the charge transport properties are relatively insensitive to X-. A thermochemical analysis (Born-Haber cycle) indicates that the energetics of [Si(Pc)O]n doping with Br2, I2, and NO+X- are surprisingly similar. The small magnitude of the band structure-counterion interactions in the {[Si(Pc)O]Xy}n materials is attributed both to the local electronic and molecular structure of the phthalocyanine subunits as well as the overall stacking rigidity imposed by the -(Si-O-)n chains.",
author = "Tamotsu Inabe and Gaudiello, {John G.} and Moguel, {Michael K.} and Marks, {Tobin J} and Burton, {Robert L.} and McCarthy, {William J.} and Kannewurf, {Carl R.} and Marks, {Tobin J.}",
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TY - JOUR

T1 - Cofacial assembly of partially oxidized metallomacrocycles as an approach to controlling lattice architecture in low-dimensional molecular "metals". Probing band structure-counterion interactions in conductive [M(phthalocyaninato)O]n macromolecules using nitrosonium oxidants

AU - Inabe, Tamotsu

AU - Gaudiello, John G.

AU - Moguel, Michael K.

AU - Marks, Tobin J

AU - Burton, Robert L.

AU - McCarthy, William J.

AU - Kannewurf, Carl R.

AU - Marks, Tobin J.

PY - 1986

Y1 - 1986

N2 - This contribution reports an integrated chemical and physicochemical investigation of the consequences of doping the cofacially joined metallomacrocyclic polymers [M(Pc)O]n, M = Si and Ge, with the nitrosonium salts NO+X-, X- = BF4-, PF6-, and SbF6-. In the case of [Si(Pc)O]n, doped products {[Si(Pc)O]Xy}n are obtained with a limiting stoichiometry y ≃ 0.36 (essentially identical with band-fillings obtained with halogen oxidants). In contrast, NO+X- doping results in decomposition of [Ge(Pc)O]n. Upon incremental NO+X- doping of [Si(Pc)O]n, transmission infrared spectra reveal the progressive growth of electronic absorption, and transmission optical spectra reveal the formation of Pc π radical cation species. Studies of the NO+X- doping process by X-ray diffractometry suggest that it is largely inhomogeneous. Computer-assisted analysis of the {[Si(Pc)O]Xy}n powder diffraction data (aided by judiciously chosen model compounds) indicates crystal structures closely analogous to those of {[Si(Pc)O](I3)0.37}n, {[Si(Pc)O](Br3)0.37}n, Ni(Pc)(ClO4)0.40, and Ni(Pc)(BF4)0.35. The data can be indexed in the tetragonal space group P4/mcc, Z = 2, with a = 13.70 (7) Å, c = 6.58 (4) Å, phthalocyanine staggering angle = 40 (2)° (X- = BF4-); a = 13.98 (6) Å, c = 6.58 (4) Å; phthalocyanine staggering angle = 40 (2)° (X- = PF6-); a = 14.31 (4) Å, c = 6.58 (4) Å, phthalocyanine staggering angle = 40 (2)° (X̊ = SbF6-). It appears that the X- ions are disordered along c. ESR spectra reveal nearly free electron g values, in accord with the ligand-centered π radical character of the oxidation. As a consequence of the pronounced unidimensionality and minimal interaction of the carriers with heavy atoms, X-band powder ESR line widths are rather narrow (2.9-0.36 G) and decrease in the order I3- > SbF6- > PF6- > BF4-. For {[Si(Pc)O](BF4)0.36}n, the line width is virtually temperature-independent from 4 to 300 K. Variable temperature (4-300 K) static magnetic susceptibility studies of the {[Si(Pc)O]Xy}n materials reveal a small, sample-dependent Curie-like component and a Pauli-like, weakly temperature dependent contribution. Within experimental error, the Pauli-like susceptibility is independent of X-. Optical reflectivity studies of these materials reveal a plasma edge in the infrared. A Drude analysis of the data yields plasma frequency and tight-binding bandwidth parameters which are essentially independent of X-. Four-probe electrical conductivity studies of polycrystalline {[Si(Pc)O]Xy}n samples reveal a sharp increase of conductivity with increasing y. The temperature dependence of the data can be most convincingly fit to a transport model involving fluctuation-induced carrier tunneling through parabolic potential barriers that separate the high conductivity regions. As for the other collective properties, the charge transport properties are relatively insensitive to X-. A thermochemical analysis (Born-Haber cycle) indicates that the energetics of [Si(Pc)O]n doping with Br2, I2, and NO+X- are surprisingly similar. The small magnitude of the band structure-counterion interactions in the {[Si(Pc)O]Xy}n materials is attributed both to the local electronic and molecular structure of the phthalocyanine subunits as well as the overall stacking rigidity imposed by the -(Si-O-)n chains.

AB - This contribution reports an integrated chemical and physicochemical investigation of the consequences of doping the cofacially joined metallomacrocyclic polymers [M(Pc)O]n, M = Si and Ge, with the nitrosonium salts NO+X-, X- = BF4-, PF6-, and SbF6-. In the case of [Si(Pc)O]n, doped products {[Si(Pc)O]Xy}n are obtained with a limiting stoichiometry y ≃ 0.36 (essentially identical with band-fillings obtained with halogen oxidants). In contrast, NO+X- doping results in decomposition of [Ge(Pc)O]n. Upon incremental NO+X- doping of [Si(Pc)O]n, transmission infrared spectra reveal the progressive growth of electronic absorption, and transmission optical spectra reveal the formation of Pc π radical cation species. Studies of the NO+X- doping process by X-ray diffractometry suggest that it is largely inhomogeneous. Computer-assisted analysis of the {[Si(Pc)O]Xy}n powder diffraction data (aided by judiciously chosen model compounds) indicates crystal structures closely analogous to those of {[Si(Pc)O](I3)0.37}n, {[Si(Pc)O](Br3)0.37}n, Ni(Pc)(ClO4)0.40, and Ni(Pc)(BF4)0.35. The data can be indexed in the tetragonal space group P4/mcc, Z = 2, with a = 13.70 (7) Å, c = 6.58 (4) Å, phthalocyanine staggering angle = 40 (2)° (X- = BF4-); a = 13.98 (6) Å, c = 6.58 (4) Å; phthalocyanine staggering angle = 40 (2)° (X- = PF6-); a = 14.31 (4) Å, c = 6.58 (4) Å, phthalocyanine staggering angle = 40 (2)° (X̊ = SbF6-). It appears that the X- ions are disordered along c. ESR spectra reveal nearly free electron g values, in accord with the ligand-centered π radical character of the oxidation. As a consequence of the pronounced unidimensionality and minimal interaction of the carriers with heavy atoms, X-band powder ESR line widths are rather narrow (2.9-0.36 G) and decrease in the order I3- > SbF6- > PF6- > BF4-. For {[Si(Pc)O](BF4)0.36}n, the line width is virtually temperature-independent from 4 to 300 K. Variable temperature (4-300 K) static magnetic susceptibility studies of the {[Si(Pc)O]Xy}n materials reveal a small, sample-dependent Curie-like component and a Pauli-like, weakly temperature dependent contribution. Within experimental error, the Pauli-like susceptibility is independent of X-. Optical reflectivity studies of these materials reveal a plasma edge in the infrared. A Drude analysis of the data yields plasma frequency and tight-binding bandwidth parameters which are essentially independent of X-. Four-probe electrical conductivity studies of polycrystalline {[Si(Pc)O]Xy}n samples reveal a sharp increase of conductivity with increasing y. The temperature dependence of the data can be most convincingly fit to a transport model involving fluctuation-induced carrier tunneling through parabolic potential barriers that separate the high conductivity regions. As for the other collective properties, the charge transport properties are relatively insensitive to X-. A thermochemical analysis (Born-Haber cycle) indicates that the energetics of [Si(Pc)O]n doping with Br2, I2, and NO+X- are surprisingly similar. The small magnitude of the band structure-counterion interactions in the {[Si(Pc)O]Xy}n materials is attributed both to the local electronic and molecular structure of the phthalocyanine subunits as well as the overall stacking rigidity imposed by the -(Si-O-)n chains.

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