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.

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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

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9-H CDCA Metalations

+ Mn(NO3)2

100% DMPU, 1

EQVT Pyridine

110°CSmall, white

crystals

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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)

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