RUI: synthesis of core modified and PI-extended porphyrinoids

The National Science Foundation Division of Chemistry awarded the Board of Trustees of Illinois State University $521,365 on August 1, 2026, under the Research at Undergraduate Institutions (RUI) program to support the synthesis, characterization, and reactivity of carbaporphyrins and related porphyrinoid structures. Dr. Timothy Lash leads research to develop efficient synthetic routes to novel carbaporphyrin-type systems—compounds in which a carbon atom replaces one of the four nitrogen atoms found in naturally occurring porphyrins. The project proposes syntheses of azaphenaliporphyrins, hydroxynaphthiporphyrins, and quinone-fused carbaporphyrins using MacDonald-type condensations, and will develop routes to carbachlorins using cyclopropane dialdehydes as intermediates. These carbaporphyrin structures exhibit modified chromophoric properties with strong absorptions throughout the visible region and form stable complexes with catalytic metals such as palladium and rhodium, with applications in medicine, sensor development, catalysis, and advanced manufacturing. The research provides training for undergraduate and master's-level graduate students in organic synthesis and multidisciplinary scientific research. Performance takes place at Illinois State University in Normal, Illinois, with a period of performance from August 1, 2026, through July 31, 2029. This award falls under the Mathematical and Physical Sciences program (CFDA 47.049).

Abstract

DR. Timothy lash of illinois state university is exploring the synthesis, characterization, and reactivity of conjugated structures that resemble naturally occurring porphyrins. Porphyrins have applications in diverse areas, including materials science, catalysis, and medicine. True porphyrins have 4 nitrogen atoms within a central cavity that allow the structure to bind metal ions. However, an important class of related compounds called carbaporphyrins have a carbon atom in place of one of these nitrogens. Carbaporphyrins have modified properties that often complement those of naturally occurring porphyrins. This project aims to develop efficient routes to novel carbaporphyrin-type systems that have unique reactivity and unusual properties. The results will increase our understanding of fundamental chemistry concepts such as aromaticity, a feature that often leads to enhanced stability. Furthermore, carbaporphyrins act as ligands that form stable complexes with important catalytic metals such as palladium and rhodium. The properties exhibited by these systems show promise for advanced manufacturing applications including medicine, sensor development, and catalysis. These projects will provide an excellent environment for training undergraduates and MS level graduate students in the field of organic synthesis and exposes them to the multidisciplinary nature of modern scientific research. In this research, syntheses of new porphyrinoid structures by ?2 + 2? And ?3 + 1? Macdonald-type condensations is proposed, including azaphenaliporphyrins, hydroxynaphthiporphyrins, and quinone-fused carbaporphyrins. The latter structures have dramatically altered chromophores with strong absorptions throughout the visible region. A route to carbachlorins and related structures will be developed using cyclopropane dialdehydes as critical intermediates in the ?3 + 1? Methodology. The effects due to strongly electron-withdrawing units will be investigated and examples of nitrobenzo- and nitronaphthoporphyrins will be synthesized. A series of indenoporphyrin analogues will be prepared by first generating aryl substituted intermediates and carrying out oxidative cyclizations (scholl reaction) to generate the conjugated structures. Indenoporphyrins introduce competing aromatic and antiaromatic conjugation pathways and possess unusual spectroscopic properties. Insertion of phosphorus atoms into carbaporphyrin structures will be examined by either introducing a phosphole unit or a cyclopentadienyl ylide and IT is anticipated that these novel structures will exhibit unique coordination chemistry. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the foundation's intellectual merit and broader impacts review criteria.- subawards are not planned for this award.