PhD Project Title: Synthesis of non-planar heterocyclic nanographenes via CH-activation
Principal Investigator: Prof. Daniel T. Gryko
PhD Project description: Polycyclic aromatic hydrocarbons (PAHs) are important molecules with expanding applications as optoelectronic materials, commonly obtained via cross-couplings of prefunctionalized building blocks. Accordingly, C-H functionalization could offer unprecedented tools for the synthesis of hardly studied, appealing PAHs such as perylene and corranulene incorporating heteroatoms or corranulene featuring axial chirality. Indeed, the presence of axially chiral motifs on PAHs could drastically impact their physical properties providing them yet unexplored properties. Synthesis of perylene and corannulene analogs with incorporated heteroatoms will be targeted via direct arylation, radical-anions coupling and Scholl reaction.
Description of the work: ESR will perform in-depth optimizations to determine the steric/electronic factors governing these reactions. In parallel, physicochemical characterization of the new materials will allow subsequent rational design of advanced PAHs. ESR will further explore different strategies to build up perylene & corranulenes analogs via C-H arylation focusing mainly on intramolecular transformations (design of simple-linked precursors); synthetic routes such as radical-anion coupling, nucleophile-electrophile addition and Scholl reaction will be explored; 2) elucidate electronic requirements for dehydrogenative fusion; 3) investigate the optical properties of synthesized PAHs.
Relevant skills that will be considered are:
- Strong theoretical background and practical skills in organic synthesis and heterocyclic chemistry
- Good level of English proficiency (understood, spoken and written)
- Skills in scientific writing (reports, papers, etc.)
- Team spirit and collaborative predisposition
Planned secondments: “1 secondment (3 months) in University of Amsterdam and 1 secondment (3 months) in Merck