Synthesis of Supramolecular Self-assembling Macromolecular Structures

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Synthesis of Supramolecular Self-assembling
Macromolecular Structures

• Matthew B. Weiss
• 2006

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Chemistry Department Macalester College
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Goals
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Goals

• Improve yields

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Goals

• Improve yields
• Develop a purification protocol

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Goals

• Improve yields
• Develop a purification protocol
• Show successful self-assembly

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Oxadiazole Molecule
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Background Information
Balsells (2005) Loye (2003)
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Identified Variables

• Problems with protocol
• Low Yield

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Potential Self-assembly
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Acylation Reaction
dichloromethane
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Acylation Reaction
0 C
Diisopropylethylamine
dichloromethane
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Acylation Reaction
0 C
Diisopropylethylamine
dichloromethane
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Cycloaromatization
H
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Cycloaromatization
82 C Acetonitrile
H
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Cycloaromatization
82 C Acetonitrile
H
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Oxadiazole Molecules
2,5-di(thiophen-2-yl)-1,3,4-oxadiazole dithiophen oxadiazole
2,5-diphenyl-1,3,4-oxadiazole diphenyl oxadiazole
2-(furan-2-yl)-5-(thiophen-2-yl)-1,3,4-oxadiazole thiophen/furan oxadiazole
2-phenyl-5-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl oxadiazole
2-phenyl-4-t-butyl-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl-t-butyl oxadiazole
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Oxadiazole Molecules
2,5-di(thiophen-2-yl)-1,3,4-oxadiazole dithiophen oxadiazole
2,5-diphenyl-1,3,4-oxadiazole diphenyl oxadiazole
2-(furan-2-yl)-5-(thiophen-2-yl)-1,3,4-oxadiazole thiophen/furan oxadiazole
2-phenyl-5-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl oxadiazole
2-phenyl-4-t-butyl-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl-t-butyl oxadiazole
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Oxadiazole Molecules
2,5-di(thiophen-2-yl)-1,3,4-oxadiazole dithiophen oxadiazole
2,5-diphenyl-1,3,4-oxadiazole diphenyl oxadiazole
2-(furan-2-yl)-5-(thiophen-2-yl)-1,3,4-oxadiazole thiophen/furan oxadiazole
2-phenyl-5-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl oxadiazole
2-phenyl-4-t-butyl-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl-t-butyl oxadiazole
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Oxadiazole Molecules
2,5-di(thiophen-2-yl)-1,3,4-oxadiazole dithiophen oxadiazole
2,5-diphenyl-1,3,4-oxadiazole diphenyl oxadiazole
2-(furan-2-yl)-5-(thiophen-2-yl)-1,3,4-oxadiazole thiophen/furan oxadiazole
2-phenyl-5-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl oxadiazole
2-phenyl-4-t-butyl-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl-t-butyl oxadiazole
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Oxadiazole Molecules
2,5-di(thiophen-2-yl)-1,3,4-oxadiazole dithiophen oxadiazole
2,5-diphenyl-1,3,4-oxadiazole diphenyl oxadiazole
2-(furan-2-yl)-5-(thiophen-2-yl)-1,3,4-oxadiazole thiophen/furan oxadiazole
2-phenyl-5-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl oxadiazole
2-phenyl-4-t-butyl-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl-t-butyl oxadiazole
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Oxadiazole Molecules
2,5-di(thiophen-2-yl)-1,3,4-oxadiazole dithiophen oxadiazole
2,5-diphenyl-1,3,4-oxadiazole diphenyl oxadiazole
2-(furan-2-yl)-5-(thiophen-2-yl)-1,3,4-oxadiazole thiophen/furan oxadiazole
2-phenyl-5-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl oxadiazole
2-phenyl-4-t-butyl-(pyridine-3-yl)-1,3,4-oxadiazole pyridyl/phenyl-t-butyl oxadiazole
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1HNMRs of Oxadiazole Derivatives
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1HNMRs of Oxadiazole Derivatives
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1HNMRs of Oxadiazole Derivatives
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1HNMRs of Oxadiazole Derivatives
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Results of Synthesis

• The five oxadiazole molecules were successfully
  synthesized and purified with high yields
• dithiophen
• diphenyl
• thiophen/furan
• pyridyl/phenyl
• pyridyl-t-butyl/phenyl

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Macromolecular Synthesis
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Self-assembled Tetramer
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Self-assembled Dimer
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Self-assembly Procedure

• Dissolved palladium(II) chloride in acetonitrile
  at 78 C

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Self-assembly Procedure

• Dissolved palladium(II) chloride in acetonitrile
  at 78 C
• Dissolved oxadiazole molecule in acetonitrile at
  0 C

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Problems Encountered

• Extracting self-assembled macromolecules using
  deuterated solvents.

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Analysis of Macromolecule
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Future Work

• Utilize other components for ligation, such as
  PtCl2 or ReCl2.

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Future Work

• Utilize other components for ligation, such as
  PtCl2 or ReCl2.
• Assess the fluorescence of modified tetramers.

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Acknowledgments

• Dr. Ronald Brisbois
• Macalester College
• Minnesota Academy of Science
• Ms. Lois Fruen
• Breck Team Science Research

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Synthesis of Oxadiazole Derivatives for Use in
Supramolecular Assembly

• Matthew B. Weiss
• 2006

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Analysis

• Electron Impact Mass Spectroscopy (EI-MS)

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Nuclear Magnetic Resonance

• All particles have a property called spin.
• In a magnetic field, particles spin with or
  against the field.
• When excited with microwave energy, particles
  become excited and change their spin slightly.