Reinventing Benzannulations: Electro-, Photo-, and Radical Approaches for Fusing Benzene and Cyclopentadiene Rings into Polyaromatics

In this project, funded jointly by the Chemical Structure, Dynamics, & Mechanisms B and Chemical Synthesis Programs of the Division of Chemistry, Professor Igor Alabugin at Florida State University will address fundamental questions in the structure and synthesis of complex polycyclic aromatic compounds. Molecular systems that allow precise control of atomic structure and energy levels at the sub-nanospace can serve as components of opto-electronic materials, energy storage devices, sensors, transistors, solar cells, functional polymers etc.

This research aims to develop efficient synthetic approaches to complex polycyclic aromatic systems via fusions of modularly assembled precursors into new carbon-rich graphene substructures. New concepts for the design of complex ring synthesis drive this project. This work combines computational and experimental components to allow training of specialists in each area.

The project will provide researchers at the undergraduate, graduate and postdoctoral levels with an opportunity to integrate learning and discovery. The results will be disseminated through publications and outreach activities, including participation in public lectures, scientific symposia, giving talks at industries, undergraduate and graduate institutions, as well as recording educational videos.

This proposal sets out to develop new approaches to the rapid construction of functionalized polycyclic aromatics by using the residual strain of helicenes and selectively generated high-energy reactive intermediates such as antiaromatic species, excited states and vinyl radicals. Furthermore, the Alabugin research team is aiming to complement available purely hexagonal graphenic networks with selectively introduced pentagonal fusions as a way to design negatively charged carbon-rich materials.

Professor Alabugin and his co-workers will also work to expand the scope of the double-annulation reactions under study such that, in a one-pot operation, the transformation effectively converts monosubstituted benzenes into pyrenes and pyrene analogues with precisely placed functional groups and heteroatoms. If successful, this multi-faceted transformation would open up one of the most efficient examples of complex functional group-tolerant benzannulation 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.