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, Tobin J Marks, H. O. Marcy, W. J. McCarthy, C. R. Kannewurf

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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]Xyn. 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)yn 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)yn show no evidence of exceptional electronic effects attributable to the dinegative counterion.

Original languageEnglish
Pages (from-to)15-24
Number of pages10
JournalSynthetic Metals
Volume29
Issue number2-3
DOIs
Publication statusPublished - Mar 21 1989

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ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Materials Chemistry
  • Polymers and Plastics

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