summer research presentationpresentation krista balto 1. what are metal organic frameworks? •...
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Summer 2017 Research Presentation
Krista Balto
1
What are Metal Organic Frameworks?
• Networks or clusters made up of organic ligands coordinated to metals.
• These coordinated networks form porous, crystalline structures.
• The pores allows them to soak up and store high volumes of natural gas.
• The pore size of the metal organic framework determines its ability to store natural gas.
• Useful for gas storage, catalysis, drug delivery etc.
MOF-5(Zn4O(BDC)3)
2
My Research• My research specifically has been focused on
synthesizing derivatives of the 9H carbazole ligand and attempting to metalate them to Cu(NO3)2 and other various metals.
• In particular, I’ve focused on adding primary, secondary and tertiary backbones to the 9-H carbazoleligand.
• Primary Backbones X = H, CH3, CH2CH3,CH2CH2CH3, CH2CH2CH2CH3, CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH3, docecyl, octadecyl
• Secondary Backbones 2-iodo-butane, 1-iodo-2-methyl propane, 2-iodo-propane
• I was only successfully able to add the 2-iodopropane backbone to the carbazole ligand.
• Various temperatures and equivalents were used in an attempt to yield the other two secondary backbones, but these attempts were unsuccessful.
• Tertiary Backbones 1-iodo-2-methyl-butane• Various temperatures and equivalents were used in an
attempt to yield the tertiary backbone, but these attempts were unsuccessful.
9-X Carbazole
Ligand
3
6.25 EQVT
KOH/DMF
*12 hours
X = Methyl, ethyl, propyl, butyl,
pentyl, hexyl, dodecyl, octadecyl,
isopropyl
My Research
* The reaction is generally
performed at room temperature
(25°C) for primary backbones,
while adding heat (~80°C) is
necessary for secondary
backbones.
+ 1.5 EQVT
Alkyl Iodide
4
Brunner, K.; Dijken, A. V.; Börner, H.; Bastiaansen, J. J. A. M.; Kiggen,
N. M. M.; Langeveld, B. M. W. Carbazole Compounds as Host Materials
for Triplet Emitters in Organic Light-Emitting Diodes: Tuning the HOMO
Level without Influencing the Triplet Energy in Small Molecules. Journal
of the American Chemical Society 2004, 126 (19), 6035–6042.
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1(ppm)
3.0
2
2.0
5
2.0
2
1.9
9
1.9
5
1.9
7
2.0
0
2.5
1D
MS
O-d
6
3.3
9W
ate
r
Propyl
Backbone
1H NMR
5
Butyl
Backbone
1H NMR
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1(ppm)
3.0
5
2.0
3
2.0
4
2.0
4
2.0
3
2.0
3
2.0
1
2.0
0
2.5
1D
MS
O-d
6
3.3
8W
ate
r
6
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1(ppm)
3.0
3
4.0
5
2.0
3
2.1
3
2.0
0
2.0
0
2.0
1
1.9
8
2.5
0D
MS
O-d
6
3.3
8W
ate
r
Pentyl
Backbone
1H NMR
7
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1(ppm)
3.0
0
6.0
3
1.9
9
1.9
8
2.0
0
2.0
2
2.0
5
2.0
3
2.5
1D
MS
O-d
6
3.3
8W
ate
r
Hexyl
Backbone
1H NMR
8
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1(ppm)
5.9
9
1.0
2
2.1
6
2.1
6
2.0
6
2.0
4
2.5
1D
MS
O-d
6
3.3
8W
ate
r
Isopropyl
Backbone
1H NMR
9
9-X CDCA Metalations
• 9-Methyl CDCA, 9-Ethyl CDCA metalations have been unsuccessful so far due to the insolubility of the ligand.
• 9-Propyl and 9-Butyl CDCA ligand metalations have yielded crystals/sheets/crystalline powder.
• 9-Pentyl and 9-Hexyl CDCA ligands have not been metalated yet.
10
9-Butyl CDCA Metalations
100% DMA,
92°C, 12 hours
• Biggest crystals were yielded with 100%
DMF or 100% DMA at 92°C
• Crystals are insoluble in most solvents
except DMPU, DMSO and THF
+ Cu(NO3)2
These
crystals
appear to be
sheets upon
doing further
investigating.11
9-Propyl CDCA Metalations
100% DMA,
2 EQVT
Benzoic Acid
92°C
Overnight
+ Cu(NO3)2
Crystals
12
9-H CDCA Polyhedra
DMF/EtOH
(1:1)
95°C
Overnight
+ Cu(NO3)2Polyhedra
13
López-Olvera, A.; Sánchez-González, E.; Campos-Reales-
Pineda, A.; Aguilar-Granda, A.; Ibarra, I. A.; Rodríguez-Molina, B.
CO2 capture in a carbazole-Based supramolecular polyhedron
structure: the significance of Cu(Ii) open metal sites. Inorg.
Chem. Front. 2017, 4 (1), 56–64.
9-H CDCA Metalations
Ni(OAc)2
100% DMF
Powdered OutCo(OAc)2
100% DMFPurple
Crystals?
Zn(OAc)2
DMF, DMA, DMPU
Powdered Out
Mn(NO3)2
DMF, DMA, DMPU
Tiny Clear
Crystals/Powder from
DMF (110°C) and DMPU
(110°C)
14
+
Co(CO2CH3)2
100% DMF
110°C~ 3 days Purple Hexagonal
Sheets/Crystals?
• Set up experiment with various ratios of DMF/MeOH
and DMF/EtOH, still on 110°C hot plate
• Cobalt polyhedra are generally dark green/black, so
it is likely that these purple crystals are not
polyhedra.
9-H CDCA Metalations
15
9-H CDCA Metalations
+ Mn(NO3)2
100% DMPU, 1
EQVT Pyridine
110°CSmall, white
crystals
16
Future Work
• Optimize conditions for 9-Propyl CDCA and 9-Butyl CDCA crystals
• Attempt to recrystallize the ones already made to remove impurities and make the crystals larger
• Begin to metalate 9-Hexyl, 9-Pentyl CDCA Ligands
• Figure out conditions that will allow for the addition of the tertiary backbone (1-iodo-2-methyl-butane) to carbazole ligand
• Figure out conditions that will allow the two remaining secondary backbones to be added to carbazole ligand (2-iodo-butane, 1-iodo-2-methyl propane)
17
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