Daniell Mattern
Professor of Chemistry and Biochemistry
Phone Number: (662)915-5335
Email: mattern@olemiss.edu
http://www.olemiss.edu/depts/chemistry/faculty/index.php?faculty_id=10

Key Words: Organic Donor-sigma-Acceptor molecules, fatty acyl analogs of acarnidine, aromatic iodination

Research Description: Organic donor-sigma-acceptor molecules. The goal of this project is to prepare compounds containing electron- donor and electron-acceptor groups, separated by a bridge of non-conducting sigma bonds. Each "D-sigma-A" target also typically contains pendant lipid tail(s) to help the molecules assemble as an ordered Langmuir-Blodgett film, or pendant alkyl thiol(s), sulifde(s), or disulfide(s) to help them assemble as an ordered monolayer on a gold surface. Such films may serve to rectify electrical current in molecule-sized circuits, which could lead to tiny electrical devices. In fact, one of our products, utilizing a pyrene donor group and a dinitrobenzyl acceptor group, displays striking rectifying voltage properties when tested as a multilayer. Our current work involves (1) making new D-sigma-A targets via further elaboration of the good donor pyrene; (2) forming the sigma bridge via Diels Alder reactions between donor-dienes and acceptor-dienophiles; (3) using anhydride chemistry to attach sigma-A and solublizing groups at opposite ends of the annoyingly insoluble compound perylene, which can potentially be converted to either a good donor or a good acceptor; and (4) attaching three thiol tails to model donor molecules in such a way that their orientation on gold electrodes will be forced to be orthogonal. Aromatic iodination. This work investigates the direct substitution of many iodine atoms onto aromatic rings. We have developed a powerful system (I2 / H4IO6 / H2SO4) for iodinating deactivated aromatics. For example, nitrobenzene and benzoic acid can easily be pentaiodinated. However, the method fails for activated rings; the conditions are too harsh. Our future work involves moderating the reaction conditions to promote high-yield conversions in activated systems such as phenol and the xylenes. Careful 13C-NMR analysis is crucial for this work, as the iodinated products have few protons for 1H-NMR, have few functional groups for IR analysis, and have high molecular weights making mass spectrometry difficult. The iodinated products have become valuable synthetic intermediates as the use of palladium-catalyzed coupling reactions of iodoorganics with alkenes (the Heck reaction) and organotins (the Stille reaction) has grown. PushMaster Dr. Mattern is the author of the PushMasterTM electron-pushing skill-builder computer program. PushMaster runs as a HyperStudio multimedia program with the (free) HyperStudio Player. It provides patient and, most importantly, interactive practice in the crucial skill of "pushing electrons" for the understanding of fundamental organic chemistry mechanisms and reactions. PushMaster is currently available on the Ole Miss campus for the Macintosh platform.

Honors Theses:

Kessler, Raegan Elise (2022) The Synthesis and Analysis of an EDTA Based Anionic Gemini Surfactant

Tiwari, Nickie (2021) Synthesis of Halogenated Glyoximes (full text)

Lybrand, Anthony (2021) Effects of Halogen Bonding on 13C NMR Shifts of Various Tolan Species (full text)

Stark, Michael Cashen (2021) Preparation of Perylene Bisimide Acceptors with Ethylcarboxyl and Pyrenylcyclohexyl Imide Groups (full text)

Peltan, Joshua (2021) One-Pot Synthesis of Disubstituted Primary Amines from Nitriles Via Grignard Addition and Metal-Alcohol Reduction (full text)

Crumpler, Reece (2020) 13C NMR Substituent Effects on para-Substituted Tolans: Using Deuteration to Assign 13C Signals in Methyltolan (full text)

Crawford, Kaci B (2019) Studies Related to Chemical Changes in Biochar. I. Polyacrylonitrile Internal Standard to Assess Chemical Changes in Graphene Oxide. II. Ultrasonic Effects on Polycyclic Aromatic Hydrocarbons as Models for Biochar (full text)

Frederick, Tarrah (2019) Preparation of a Perylenebisimide Acceptor with Serinol and Nonadecyl-Swallowtail Imides for Use in Molecular Rectification (full text)

Long, James (2019) Effects of Halogen Bonding on 13C NMR Shifts of Iodotolan (full text)

Nguyen, Henry (2019) Unexpected Outcomes during the Attempted Iodination of Biphenol (full text)

Fan, Alex (2017) Iodination of 3,5-Dichloroanisole Using Silver Salts. (full text)

May, Bobby (2017) Towards the Synthesis of a Polyamine Perylenebisimide Derivative for Intercalation into Quadruplex DNA. (full text)

Barnett, Christopher Carter (2015) An Investigation into the Synthesis of a Four-Armed Diamino Swallowtail. (full text)

Whicker, Wyatt S (2015) Towards the Synthesis of a Swallowtailed Perylene Monoimide. (full text)

Gilbert, Dakota (2014) An Investigation Into Polyiodination of Activated Benzene Derivatives with Electrophilic Aromatic Substitution Reactions. (full text)

Palmer, Andrew (2014) Investigation into the Synthesis of Dodecahydro-3a,9a-diazaperylene. (full text)

Spurlock, Brian (2014) Synthesis of an Unsymmetrical CCC-NHC Pincer Ligand Precursor. (full text)

Eader, Granison Edward (2013) "The Activation and Reaction of a Persistent Carbene Dimer"

Matrick, Andrew Jacob (2013) "Polycationic Perylenebisimides for G-Quadruplex Binding" (full text)

Wilson, Jonathon Dillon (2013) "Synthesis of 2-(2-phenylethyl)propane-1,3-dithiol as a Gold Nanoparticle Ligand"

Russell, Brandon Skylur (2008) "The Link Between DNA Lesion Formation and Cytotoxicity in Human HCT116 Cells Exposed to Toxic Levels of Nitric Oxide"

Sindelar, Robert William (2003) "The Total Synthesis of Acarnidine"

Crowson, Mary Claire (2002) "Synthesis of Biotinylated Compounds for Use in Biological Systems: Initial Study"