1. Nitrogenated Covalent Organic Frameworks
2017
Veronica Spaulding
Hoberg and Parkinson Groups

2. Overview
Introduction – Background on Graphene: Structure and Applications
Project Outline – Synthetic Goal and Theory
Getting the Right Materials – Synthesis of Starting Reagents
Polymer Synthesis – Creating the Polymer
Concepts Learned – Techniques and Progress

3. Introduction Graphene – Structure Benzene Graphite
Graphene is a two-dimensional single atomic layer of graphite; an abundant mineral which is an allotrope of carbon that is made up of very tightly bonded carbon atoms organized into a hexagonal lattice. What makes graphene so special is its sp2 hybridization and very thin atomic thickness (of 0.345Nm). 
Graphite

4. pubs.rsc.org/services/images

5. Graphene Characteristics Drawbacks 2D- Thin (0.345 nm)
It conducts heat, electricity, and is virtually transparent.
Unique elastic, filtration, and optical properties useful in other areas of science.
Drawbacks
Limited functionalization
Random pores “Defects”
Pore size inconsistency
Pore homogeneity – “Chemical Sameness”
Expensive
Ultimate tensile strength of 130,000,000,000 Pascals
Examples are making touch screens more durable
Used in Solar Cells
Used in the production of lithium-ion batteries that recharge faster. These batteries use graphene on the anode surface.
Low  cost  water  desalination  by  using  graphene-with  holes  the  size  of  a  nanometer  to  remove  ions  from  water.
Columbia University said it would take an elephant balanced on a pencil to puncture a graphene sheet with the same thickness as Saran Wrap
© (Accessed 07/05/2016)

6. Nitrogenated Holey 2D Structures
Alternatives:
The substitution of nitrogen (N) atoms appears to be an excellent choice.
Small atomic size
Greater electronegativity
Five-electron valence structure (sp2 hybridization) allow it to naturally fit into a strong covalent network structure of carbon atoms.
Results:
Significantly stronger interactions than graphite (layered version of graphene).
TEM characterization of these compounds show high crystallinity.
XRD shows that the structure was thinner than graphene at nm.
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase identification of a crystalline material and can provide information on unit cell dimensions. The analyzed material is finely ground, homogenized, and average bulk composition is determined.
Transmission electron microscopy (TEM) is a microscopy technique in which a beam of electrons is transmitted through an ultra-thin specimen, interacting with the specimen as it passes through it
Mahmood, J. et al.Nitrogenated holey two-dimensional structures. Nat. Commun.6:6486 doi: /ncomms7486 (2015).

7. Condensation Reaction

8. Mahmood, J. et al. Nitrogenated holey two-dimensional structures. Nat
Mahmood, J. et al.Nitrogenated holey two-dimensional structures. Nat. Commun.6:6486 doi: /ncomms7486 (2015).

9. STM Characterization
Scanning Tunneling Microscope used to look at atoms
Mahmood, J. et al.Nitrogenated holey two-dimensional structures. Nat. Commun.6:6486 doi: /ncomms7486 (2015).

10. Self-assembled polymer with characteristics that:
Project Outline
Self-assembled polymer with characteristics that:
Can be widely functionalized
Has ordered pores
Has pore heterogeneity
Different sized pores possible
ChemCalc: a building block for tomorrow’s chemical infrastructure. Patiny, Luc; Borel, AlainJournal of Chemical Information and Modeling 2013. DOI:  /ci300563h

11. Getting the Right Materials
1,2-Diamino-4,5- Ditosylamidobenzne
Hexaketocyclohexane Octahydrate

12. 1,2-Diamino-4,5-Ditosylamidobenzene
1,2-Diaminobenzene  1,2-Ditosylamidobenzene  1,2-Dinitro-4,5-ditosylamidobenzne  1,2-Diamino-4,5-Ditosylamidobenzene
Proc: Chem. Eur. J. 2014, 20,

13. Hexaketocyclohexane Octahydrate
Glyoxal  Sodium Tetrahydroxyquinone  Hexaketocyclohexane Octahydrate
Proc: Step 1 – Organic Synthesis, Coll. Vol 5., p.1011(1973); Vol.42, p.90 (1962). Step 2 – J.Org. Chem. 1986, 51,

15. Synthetic Step 1

16. HNMR 07/12/16
Methyl Tosyl H
Tosyl H
Amino H

17. Synthetic Step 2

18. Self-Assemble Polymer

20. Transmission Electron Microscopy: Nitrogenated Covalent Organic Framework
TEM performed by Josh T. Stecher: Hoberg group 2016

21. Into the Future So what does this mean for science industries?
Graphene has over 20,000 patents even with its limitations
This project could essentially replace Graphene
Revolutionize everyday materials (such as typical membrane filters).
Room Temperature Hydrogen Storage

22. Techniques Learned and Improved
Organic Synthesis Trial and Error
Rotovap
C13&H - NMR (400hz)
Maldi Characterizations
Large Scale Reactions
Recrystallizations
IR Characterization
Hydrogenation Reaction w/ Catalyst
Extractions
Reflux and Condensation Reactions
Teamwork

23. FIN
Men love to wonder, and that is the seed of science.  -Emerson
Questions?

24. THANK YOU! Funding: WRSP NASA REU MCNAIR Hoberg/ParkinsonGroup
Project Group:
Jeremie Adams
Jordan Brophy
Dr. Hoberg
Dr. Parkinson
Josh Stecher
Katie Li
Johnathan Kephart

25. Polymer Synthesis
The basics of this synthesis is dependent on this amine condensation reaction.
Starting with an acid catalyzed reaction the nitrogen will be attracted to the positive charge on the carbonyl carbon atom.
The oxygen and nitrogen prefer to have negative charges. Nitrogen will lose a hydrogen atom. Oxygen will gain a hydrogen and act as a leaving group (H2O) when electrons from nitrogen form a double bond with the positively charged carbon. Nitrogen will then lose a hydrogen to regain electrons for a stable charge.

26. Reaction of HKH and 1,2-Diamino-4,5-Ditosylamidobenzene
In a round bottom flask add 3.3 equivalence of the 1,2-Diamino-4,5- ditosylamidobenzene solid and 1 equivalence of the Hexaketocyclohexane Octahydrate. Dissolve in glacial acetic acid, attach round bottom to the condenser. Let reflux for 4 hours. Add water to precipitate solid, vacuum filter product while hot.

27. Alt. Synthetic Step 2
Brominate the sites ortho to tosyl groups, each spot is activated by the surrounding nitrogens.
The outer Benzene rings can undergo electrophilic aromatic substitution and attack Bromine.

28. Alt. Synthetic Step 2.5
Coupling via Palladium Catalyst and