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

Research output: Contribution to journalArticlepeer-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]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

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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