3rd year seminar
TRANSCRIPT
Fullerenes,
Building Blocks of MOFs?!
Amineh Aghabali3rd year seminar
April 2014, UC-DAVIS
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Fullerenes
• Properties and Applications
MOFs
• Properties and Applications
In this research
• IDEA!
• Experimental part
• Challenges
• results
Future work
Table of contents
FullerenesDiscovery1◦ In 1985 by mass spectroscopy ◦ Named after Richard Fuller
1. Nature 1985, 318, 162
◦ Nobel prize (1996)
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FullerenesProperties and applications1
Pronounced Redox activityAcceptor in D-A dyadsPhotovoltaic devicesSuperconductors
Anti HIV activityTumor treatment
Daily usage!
1. Nature materials, 2010, 9, 8682. https://www.shinsoskincare.com/essence.php
125 times more effective at protecting the skin from harmful free radicals than Vitamin ester C
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Metal Organic FrameworksMOFs compounds consisting of metal ions or clusters coordinated to often rigid organic molecules to form 1,2,3- D structures
New J. Chem., 2010, 34, 23665
Properties:Similar to zeolites but much more diversePorous• Gas storage• Fuel storage• SensorsHigh surface areaCatalysis Conductivity?
New J. Chem., 2010, 34, 2366
Metal Organic Frameworks
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In this Research …
IDEAFullerenes as building blocks of MOFs
To mix properties of the two families and create unique new characteristics!
Metal-Fullerene Framework(MFF)
Metal
controlled coordination?
Fullerene ( ligand)
Functionalization
At least bidentate8
Controlled coordination to metals:
J.Chem.Soc.Rev 2009, 38, 1400
Secondary building blocks
Inorg. Chem. 2002, 41, 2903
IDEA
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Fullerene functionalization:Some of ligands used in MOF chemistry
J.Chem.Soc.Rev 2009, 38, 1400
Nitrogenous linkers Oxygen linkers
IDEA
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ExperimentN N
HN NH
hν, 24 hoursN2 Atmosphere
Main product%46 yield
Angew. Chem. Int. Ed. 1993, 32, 1174Tetrahedron 1996, 5021
Bidentate nitrogenous ligand
N N
M M
O O
OO
O O
R
R
R
R
+
R: CH3, CF3
M: Rh, Cu, Mo
…..Self-Assembly
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Analysis
N N
M M
O O
OO
O O
R
R
R
R
1,2-dichloromathaneChlorobenzene
chloroformBenzeneToluene
CS2
MethanolEthanolBenzeneAcetone
CS2
Best method for product characterizations: SCXRD!
Slow evaporationVapor diffusionSolvothermal techniqueLiquid-liquid diffusion
After months of trying different systems, there was a single crystal!
M=Cu, Rh, Mo
R=CH3, CF3
Crystallization
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Results
Strong electron density not resolved!Crystals from different solvent systemsData collections on home instrument and synchrotronChecked by expert crystallographers
MFF? YES
Reportable? NO!
C60.Piperazine +Rh2(TFA)2
Space group: PbcmR=14% !
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Challenge Accepted!
Angew. Chem. Int. Ed. 2010, 49, 4829J. Chem. Res. 1997, 442, 2647
triptycene
Anthracene dimer
N N
M M
O O
OO
O O
R
R
R
R
There is something which makes the crystal unhappy!
Literature review…
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Crystallographic info
Space group Pnma
a (Å) 15.78
b (Å) 19.35
c (Å) 18.89
Z 8
V (Å3) 4858
R1 %3.2
Rh-N bond(Å) 2.467
Where is Anthracene dimer/triptycene?
MFF? YES
Reportable? YES
Results
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Results
Crystallographic infoSpace group Pnma
a (Å) 19.24
b (Å) 19.68
c (Å) 19.91
Z 4
V (Å3) 7543
R1 %6.0
Rh-N bond(Å) 2.48016
C70
Other fullerenes (C70)?
Crystallographic info
Space group Pmma
a (Å) 19.69
b (Å) 15.80
c (Å) 12.80
Z 4
V (Å3) 3986
R1 --
Results
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Results (Temperature Studies) C r y sta l l ograph i c i n fo
Temp (K) 90 100 23
Space group Pnma Pnma Pnma
a (Å) 19.24 19.31 19.38
b (Å) 19.68 19.73 19.80
c (Å) 19.91 19.96 20.02
Z 4 4 4
V (Å3) 7543 7607 7691
R1 %6.0 %8.3 %8.0
Rh-N bond(Å) 2.480 2.493 2.510
T=90 K
T=100 K
T=r.t.
Rh-N distance
197 hits in CSD
Ma
x:
2.4
38
(Å
)
Longest Rh-N bond distance in Rh acetate dimer complexes with nitrogenous ligands
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Conclusion and Future Works1-D metal fullerene frameworkEasy/high yield fullerene functionalizationSelf-assemblyGreat directionalityRoom temperature stability
2 and 3- dimensional MFF?
Future workproperties• Thermal conductivity• Resistivity
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AcknowledgementProf. Alan BalchProf. Marilyn Olmstead
My labmates:-Faye Claire Ph.D.-Evan Sarina-Melissa Rivera-Kellie England-Kamran Ghiassi-Daniel Walters
Our Undergrads:-Kaifeng Liang-Syazana Hisham