PhD, University of Florida, Chemistry (2021)
B.S., Florida Institute of Technology, Biochemistry (2016)
Zhenan Bao, Postdoctoral Research Mentor
Zhenan Bao, Postdoctoral Faculty Sponsor
Tuning Supramolecular Polymer Assembly through Stereoelectronic Interactions.
Journal of the American Chemical Society
The supramolecular polymerization of 2,11-dithia[3.3]paracyclophanes through self-complementary intermolecular and transannular amide hydrogen bonding is presented. An n pi* interaction between the amide hydrogen bonding units and the central bridging atom results from the single-point exchange of a carbon atom for a sulfur atom. This orbital donor-acceptor interaction can be strengthened by oxidizing the sulfide to a sulfone which acts to shorten the donor···acceptor distance and increase orbital overlap. Experimental signatures of the increased n pi* interaction include larger isodesmic polymerization elongation constants in solution, changes in characteristic bond stretching frequencies, and geometric/structural changes evaluated by X-ray crystallography. The experimental data are supported by extensive computational investigations of both assembling and nonassembling 2,11-dithia[3.3]paracyclophanes as well as a rationally designed model system to confirm the role of stereoelectronic effects on supramolecular polymer assembly.
View details for DOI 10.1021/jacs.1c05522
View details for PubMedID 34346675