Campus Units
Chemistry
Document Type
Article
Publication Version
Submitted Manuscript
Publication Date
2-18-2020
Journal or Book Title
The Journal of Organic Chemistry
DOI
10.1021/acs.joc.9b03289
Abstract
Manipulating frontier orbital energies of aromatic molecules with substituents is key to a variety of chemical and material applications. Here, we investigate a simple strategy for achieving high-energy in-plane orbitals for aromatics simply by positioning iodine atoms next to each other. The lone pair orbitals on the iodines mix to give a high-energy in-plane σ-antibonding orbital as the highest occupied molecular orbital (HOMO). We show that this effect can be used to manipulate orbital gaps, the symmetry of the highest occupied orbital, and the adopted electronic state for reactive intermediates. This electronic effect is not limited to reactive intermediates, and we demonstrate that this iodine buttressing strategy also can be used to achieve small HOMO–lowest unoccupied molecular orbital (HOMO–LUMO) gaps in organic electronic materials. Iodinated oligomers of several of the most popular conducting polymers are computed to have smaller HOMO–LUMO gaps than the unsubstituted materials. This iodine buttressing approach for generating high-energy in-plane HOMOs is anticipated to be highly general. While the unusual properties of fluorous materials are well established, at the other extreme on the periodic table novel properties of iodous materials may await discovery.
Copyright Owner
American Chemical Society
Copyright Date
2020
Language
en
File Format
application/pdf
Recommended Citation
Qiu, Yunfan and Winter, Arthur, "Anomalous Electronic Properties of Iodous Materials: Application to High-Spin Reactive Intermediates and Conjugated Polymers" (2020). Chemistry Publications. 1214.
https://lib.dr.iastate.edu/chem_pubs/1214
Comments
This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Organic Chemistry, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.joc.9b03289. Posted with permission.