Highly conductive metallomacrocyclic assemblies. Synthetic approaches to molecular metals with variable band-filling

John G. Gaudiello, Henry O. Marcy, William J. McCarthy, Michael K. Moguel, Carl R. Kannewurf, Tobin J Marks

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Abstract

The enforced cofacial structure of the polymer [Si(Pc)O]n has been employed to introduce new oxidation states in phthalocyanine molecular metals. Thus, oxidative electrochemical techniques have produced materials with doping levels as high as {[Si(Pc)O](BF4)0.50}n, {[Si(Pc)O] (p-toluene-sulfonate)0.85}n and {[Si(Pc)O](SO4)0.09}n. Controlled potential coulometry and X-ray diffraction studies of the [Si(Pc)O]n/BF4 - system suggest that 'break-in' phenomena have a structural basis (orthorhombic → tetragonal) and that doping is relatively homogeneous. Optical, magnetic, and charge transport properties of the {[Si(Pc)O](BF)4y}n series are reported as a function of y. Electrochemical techniques have also been employed to synthesize partially reduced polymers such as {(Et4N)0.25[Si(Pc)O]}n and {[Li0.25[Si(Pc)O]}n. Incremental doping of [Si(Pc)O]n with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) produces materials with doping levels as high as {[Si(Pc)O]DDQy}n, y = 0.91. Optical and charge transport measurements show that as y is progressively increased, the polymer is transformed from a filled band insulator (y = 0.00), to a molecular metal (y ≈ 0.30 - 0.50), to an integral oxidation state Mott insulator (y {greater-than or approximate} 0.90).

Original languageEnglish
Pages (from-to)115-128
Number of pages14
JournalSynthetic Metals
Volume15
Issue number2-3
DOIs
Publication statusPublished - 1986

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ASJC Scopus subject areas

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

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