Conducting%20Polyrotaxane:%20Synthesis%20and%20Potential%20Applications

1
Conducting Polyrotaxane Synthesis and Potential
Applications

• Phoebe Kwan
• Swager Group
• MIT Department of Chemistry

2
Electronic Polymers a Gain Medium
Non-Linearity Responses(Amplification) From
Transport Properties
Energy Migration
Exponential Increases
Initial Report Zhou, Swager J. Am. Chem. Soc.
1995, 117, 12593 Ions Kim, McQuade, McHugh,
Swager, Angew. Chem. 2000, 39, 3868 Crawford,
Goldfinger, Swager J. Am. Chem. Soc. 1998, 120,
5187 TNT Yang, Swager J. Am. Chem. Soc. 1998,
120, 5321 FRET Levitsky, Kim, Swager J. Am.
Chem. Soc. 1999, 121, 1466 McQuade, Hegedus,
Swager,J. Am. Chem Soc. 2000, 122, 12389
McQuade, Pullen, Swager, Chem. Rev. 2000, 100,
2537-2574
Recent Works by Heeger, Schanze, Whitten,
McBranch, Bazan, Wasielewski, Kimura,
Ajayaghosh, Sailor
3
Conducting Transition Metal Hybrid Polymers

• Why Use Transition Metal Hybrid Materials?
• Metals Bind to Anions, Lewis Bases, and Gases
• Electrocatalysis, Magnetism
• Fluxional Properties-Allosterism, Actuation

4
The Role of Metal Ions
M
5
Design Principle
Tetrahedral cavity allows binding of metal ion
14Å
M
Highly conducting Conjugated backbone
Bulky stopper prevents stacking (aggregation) of
conducting wires
6
Synthesis 1
7
Synthesis 2
8
Synthesis 3
9
PM3 Geometry Optimization by Spartan
10
PM3 Geometry Optimization by Spartan
11
Molecular Modeling
12
Molecular Modeling
13
Future Directions

• Prepare robust polymer thin films for
  electrochemical studies.
• Investigate electrical, chemical and magnetic
  properties of various metallorotaxanes.
• Test polymers as sensory materials for a variety
  of analytes, such as nitric oxide and fluoride
  ions.
• Create configurable memory devices.