synthesis of supramolecular self-assembling macromolecular structures
DESCRIPTION
Synthesis of Supramolecular Self-assembling Macromolecular Structures. Matthew B. Weiss 2006. Chemistry Department Macalester College. Goals. Goals. Improve yields. Goals. Improve yields Develop a purification protocol. Goals. Improve yields Develop a purification protocol - PowerPoint PPT PresentationTRANSCRIPT
Synthesis of Supramolecular Self-assembling
Macromolecular Structures Matthew B. Weiss
2006
Chemistry Department Macalester College
Goals
Goals• Improve yields
Goals• Improve yields
• Develop a purification protocol
Goals• Improve yields • Develop a purification protocol• Show successful self-assembly
Oxadiazole Molecule
Background Information
Balsells (2005)
Loye (2003)
Identified Variables
• Problems with protocol
• Low Yield
Potential Self-assembly
N
N
O
NN
N
O
N
P d
N
N
O
N N
N
O
N
P d
P d
P d
C l
C l
C l C l
C l C l
C l
C l
Acylation Reaction
dichloromethane
Acylation Reaction
Diisopropylethylamine
0 °C
dichloromethane
Acylation Reaction
Diisopropylethylamine
0 °C
dichloromethane
Cycloaromatization
H
Cycloaromatization
82 °C Acetonitrile
H
Cycloaromatization
82 °C Acetonitrile
H
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
NN
O
N
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
NN
O
N
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
NN
O
N
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
NN
O
N
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
NN
O
N
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
NN
O
N
1HNMRs of Oxadiazole Derivatives
1HNMRs of Oxadiazole Derivatives
1HNMRs of Oxadiazole Derivatives
1HNMRs of Oxadiazole Derivatives
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
Macromolecular Synthesis
N
N
O
NN
N
O
N
P d
N
N
O
N N
N
O
N
P d
P d
P d
C l
C l
C l C l
C l C l
C l
C l
Self-assembled Tetramer
N
N
O
NN
N
O
N
P d
N
N
O
N N
N
O
N
P d
P d
P d
C l
C l
C l C l
C l C l
C l
C l
Self-assembled Dimer
N
N
O
NN
N
O
N
P d
N
N
O
N N
N
O
N
P d
P d
P d
C l
C l
C l C l
C l C l
C l
C l
N N
O N
NN
ON
P d P dC lC l
C l
C l
Self-assembly Procedure
• Dissolved palladium(II) chloride in acetonitrile at 78 °C
Self-assembly Procedure
• Dissolved palladium(II) chloride in acetonitrile at 78 °C
• Dissolved oxadiazole molecule in acetonitrile at 0 °C
Problems Encountered
• Extracting self-assembled macromolecules using deuterated solvents.
Analysis of Macromolecule
Future Work
• Utilize other components for ligation, such as PtCl2 or ReCl2.
Future Work
• Utilize other components for ligation, such as PtCl2 or ReCl2.
• Assess the fluorescence of modified tetramers.
Acknowledgments• Dr. Ronald Brisbois
• Macalester College
• Minnesota Academy of Science
• Ms. Lois Fruen
• Breck Team Science Research
Synthesis of Oxadiazole Derivatives for Use in
Supramolecular AssemblyMatthew B. Weiss
2006
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.