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.
| Original language | English |
|---|---|
| Pages (from-to) | 15-24 |
| Number of pages | 10 |
| Journal | Synthetic Metals |
| Volume | 29 |
| Issue number | 2-3 |
| DOIs | |
| Publication status | Published - Mar 21 1989 |
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ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Materials Chemistry
- Polymers and Plastics
Cite this
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, Tobin 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
}
TY - JOUR
T1 - Electrochemistry of cofacial phthalocyanine polymers
T2 - What can we learn about how molecular metal collective properties respond to wide variations in band filling?
AU - Kellogg, G. E.
AU - Gaudiello, J. G.
AU - Schlueter, J. A.
AU - Tetrick, S. M.
AU - Marks, Tobin J
AU - Marcy, H. O.
AU - McCarthy, W. J.
AU - Kannewurf, C. R.
PY - 1989/3/21
Y1 - 1989/3/21
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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UR - http://www.scopus.com/inward/citedby.url?scp=0024626281&partnerID=8YFLogxK
U2 - 10.1016/0379-6779(89)90873-4
DO - 10.1016/0379-6779(89)90873-4
M3 - Article
VL - 29
SP - 15
EP - 24
JO - Synthetic Metals
JF - Synthetic Metals
SN - 0379-6779
IS - 2-3
ER -