| Name | Mr. Cole Stearns |
|---|---|
| Email hidden; Javascript is required. | |
| Organization | University of Florida |
| Position | Graduate Student |
| Invited | No |
| Type | Oral |
| Topic | Organic Chemistry |
| Title | Self-Assembling Properties of Hybrid-Deck [2.2]Paracylophanes |
| Author(s) | Cole D. Stearns, Ajeet Kumar, Will R. Henderson, Khalil A. Abboud, and Ronald K. Castellano* |
| Author Location(s) | Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL 32611-7200, USA |
| Abstract | [2.2]Paracyclophanes ([2.2]pCps) have been widely studied for decades due to their unique reactivity, optical properties, and stereoelectronics, with many applications in donor-acceptor complexes, thin-film devices, and organocatalysis. However, [2.2]pCps, unlike many other π-systems, have been virtually unexplored in a supramolecular context, and the first [2.2]paracyclophane supramolecular polymers ([2.2]pCpSPs) were reported by our group in 2016 using a [2.2]paracyclophane-tetracarboxamide ([2.2]pCpTA) monomer. Early iterations of [2.2]pCpSPs demonstrated that the core [2.2]pCp scaffold affords distinct π-interactions, intramolecular H-bonding, and steric effects that are unique within the field at large. Further experimentation in our group has shown that macrodipoles, H-bonding geometries, and amide connectivity of [2.2]pCpTAs are critical variables in dictating strong, cooperative supramolecular polymerization. In this work, we target these variables by synthesizing a library of tetrasubstituted hybrid-deck [2.2]pCps. These novel derivatives each have unique bis-(anilide) and bis-(carboxamide) functionalization and regiochemistry that are expected to have significant effects on the dipole, polymerization mechanism, and assembly strength of the resultant [2.2]pCpSPs. Various solution studies, X-ray crystallography, and density functional theory (DFT) are performed to understand H-bonding geometry, assembly thermodynamics and mechanism, SP macrodipole, and many other parameters critical to optimizing these novel supramolecular scaffolds. |
| Date | 06/02/2023 |
| Time | 02:00 PM |
