Electrochemistry of cofacial phthalocyanine polymers: What can we learn about how molecular metal collective properties respond to wide variations in band filling?

G. E. Kellogg; J. G. Gaudiello; J. A. Schlueter; S. M. Tetrick; T. J. Marks; H. O. Marcy; W. J. McCarthy; C. R. Kannewurf

doi:10.1016/0379-6779(89)90873-4

Electrochemistry of cofacial phthalocyanine polymers: What can we learn about how molecular metal collective properties respond to wide variations in band filling?

G. E. Kellogg, J. G. Gaudiello, J. A. Schlueter, S. M. Tetrick, T. J. Marks, H. O. Marcy, W. J. McCarthy, C. R. Kannewurf

Northwestern University

Research output: Contribution to journal › Article › peer-review

3 Citations (Scopus)

Abstract

The oxidative electrochemistry of the cofacially joined phthalocyanine polymer [Si (Pc)O]_n to yield molecular "metals" with tunable band filling is described. Initial doping (oxidation) of orthorhombic [Si (Pc)O]_n is accompanied by a rearrangement to a tetragonal crystal structure. Once in the tetragonal crystal structure, the conduction band filling can be continuously varied (i.e. doping is homogeneous) over a broad range in y for {[Si (Pc)O]X_y∼_n. For example, materials incorporating BF^-₄ as the counterion can be tuned between y = 0.0 and y = 0.50. In fact, the maximum doping level obtainable with a given counterion is largely a function of anion size. Charge transport, optical, and magnetic studies of the {[Si (Pc)O] (BF₄)_y∼_n materials reveal an evolution in properties from insulator/semiconductor-like to metal-like with increasing y and an abrupt insulator-to-metal transition at y ≈ 0.20. This change at y ≈ 0.20 appears to be an Anderson-like transition from localized (disordered) states to delocalized states. Physical measurements on {[Si (Pc)-O] (SO₄)_y∼_n show no evidence of exceptional electronic effects attributable to the dinegative counterion.

Original language	English
Pages (from-to)	15-24
Number of pages	10
Journal	Synthetic Metals
Volume	29
Issue number	2-3
DOIs	https://doi.org/10.1016/0379-6779(89)90873-4
Publication status	Published - Mar 21 1989

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Condensed Matter Physics
Mechanics of Materials
Mechanical Engineering
Metals and Alloys
Materials Chemistry

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Kellogg, G. E., Gaudiello, J. G., Schlueter, J. A., Tetrick, S. M., Marks, T. J., Marcy, H. O., McCarthy, W. J., & Kannewurf, C. R. (1989). Electrochemistry of cofacial phthalocyanine polymers: What can we learn about how molecular metal collective properties respond to wide variations in band filling? Synthetic Metals, 29(2-3), 15-24. https://doi.org/10.1016/0379-6779(89)90873-4

Electrochemistry of cofacial phthalocyanine polymers : What can we learn about how molecular metal collective properties respond to wide variations in band filling? / Kellogg, G. E.; Gaudiello, J. G.; Schlueter, J. A.; Tetrick, S. M.; Marks, T. J.; Marcy, H. O.; McCarthy, W. J.; Kannewurf, C. R.

In: Synthetic Metals, Vol. 29, No. 2-3, 21.03.1989, p. 15-24.

Research output: Contribution to journal › Article › peer-review

Kellogg, GE, Gaudiello, JG, Schlueter, JA, Tetrick, SM, Marks, TJ, Marcy, HO, McCarthy, WJ & Kannewurf, CR 1989, 'Electrochemistry of cofacial phthalocyanine polymers: What can we learn about how molecular metal collective properties respond to wide variations in band filling?', Synthetic Metals, vol. 29, no. 2-3, pp. 15-24. https://doi.org/10.1016/0379-6779(89)90873-4

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title = "Electrochemistry of cofacial phthalocyanine polymers: What can we learn about how molecular metal collective properties respond to wide variations in band filling?",

abstract = "The oxidative electrochemistry of the cofacially joined phthalocyanine polymer [Si (Pc)O]n to yield molecular {"}metals{"} with tunable band filling is described. Initial doping (oxidation) of orthorhombic [Si (Pc)O]n is accompanied by a rearrangement to a tetragonal crystal structure. Once in the tetragonal crystal structure, the conduction band filling can be continuously varied (i.e. doping is homogeneous) over a broad range in y for {[Si (Pc)O]Xy∼n. For example, materials incorporating BF-4 as the counterion can be tuned between y = 0.0 and y = 0.50. In fact, the maximum doping level obtainable with a given counterion is largely a function of anion size. Charge transport, optical, and magnetic studies of the {[Si (Pc)O] (BF4)y∼n materials reveal an evolution in properties from insulator/semiconductor-like to metal-like with increasing y and an abrupt insulator-to-metal transition at y ≈ 0.20. This change at y ≈ 0.20 appears to be an Anderson-like transition from localized (disordered) states to delocalized states. Physical measurements on {[Si (Pc)-O] (SO4)y∼n show no evidence of exceptional electronic effects attributable to the dinegative counterion.",

author = "Kellogg, {G. E.} and Gaudiello, {J. G.} and Schlueter, {J. A.} and Tetrick, {S. M.} and Marks, {T. J.} and Marcy, {H. O.} and McCarthy, {W. J.} and Kannewurf, {C. R.}",

note = "Funding Information: ACKNOWLEDGEMENTS We acknowledge the support of the Office of Naval Research and NSF through the Materials Research Center of Northwestern University (Grant DMR85-20280).",

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AU - Kellogg, G. E.

AU - Gaudiello, J. G.

AU - Schlueter, J. A.

AU - Tetrick, S. M.

AU - Marks, T. J.

AU - Marcy, H. O.

AU - McCarthy, W. J.

AU - Kannewurf, C. R.

N1 - Funding Information: ACKNOWLEDGEMENTS We acknowledge the support of the Office of Naval Research and NSF through the Materials Research Center of Northwestern University (Grant DMR85-20280).

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N2 - The oxidative electrochemistry of the cofacially joined phthalocyanine polymer [Si (Pc)O]n to yield molecular "metals" with tunable band filling is described. Initial doping (oxidation) of orthorhombic [Si (Pc)O]n is accompanied by a rearrangement to a tetragonal crystal structure. Once in the tetragonal crystal structure, the conduction band filling can be continuously varied (i.e. doping is homogeneous) over a broad range in y for {[Si (Pc)O]Xy∼n. For example, materials incorporating BF-4 as the counterion can be tuned between y = 0.0 and y = 0.50. In fact, the maximum doping level obtainable with a given counterion is largely a function of anion size. Charge transport, optical, and magnetic studies of the {[Si (Pc)O] (BF4)y∼n materials reveal an evolution in properties from insulator/semiconductor-like to metal-like with increasing y and an abrupt insulator-to-metal transition at y ≈ 0.20. This change at y ≈ 0.20 appears to be an Anderson-like transition from localized (disordered) states to delocalized states. Physical measurements on {[Si (Pc)-O] (SO4)y∼n show no evidence of exceptional electronic effects attributable to the dinegative counterion.

AB - The oxidative electrochemistry of the cofacially joined phthalocyanine polymer [Si (Pc)O]n to yield molecular "metals" with tunable band filling is described. Initial doping (oxidation) of orthorhombic [Si (Pc)O]n is accompanied by a rearrangement to a tetragonal crystal structure. Once in the tetragonal crystal structure, the conduction band filling can be continuously varied (i.e. doping is homogeneous) over a broad range in y for {[Si (Pc)O]Xy∼n. For example, materials incorporating BF-4 as the counterion can be tuned between y = 0.0 and y = 0.50. In fact, the maximum doping level obtainable with a given counterion is largely a function of anion size. Charge transport, optical, and magnetic studies of the {[Si (Pc)O] (BF4)y∼n materials reveal an evolution in properties from insulator/semiconductor-like to metal-like with increasing y and an abrupt insulator-to-metal transition at y ≈ 0.20. This change at y ≈ 0.20 appears to be an Anderson-like transition from localized (disordered) states to delocalized states. Physical measurements on {[Si (Pc)-O] (SO4)y∼n show no evidence of exceptional electronic effects attributable to the dinegative counterion.

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