GRAPHYRIN · Development of bottom-up custom-functionalized graphene/porphyrin nanoarchitectures with atomic precision

The ongoing miniaturization of electronic devices has been raising awareness for the need to develop alternative high-performance and energy-efficient semiconductor materials. The current project (GRAPHYRIN) aims to synthesize new atomically precise hybrid nanoarchitectures, comprising graphene nanostructures (graphene nanoribbons, GNRs, or nanoporous graphene, NPG) and porphyrins (PORs), with promising properties to fabricate next-generation materials to be used, for example, in gas sensing electronic devices. First, multistage organic synthesis will be carried out to obtain individual or fused precursors of GNRs and PORs (“seeding stages”), which will later allow the construction of partially and fully conjugated hybrid systems. Here, we will synthesize appropriate bianthracence-based reactants (or equivalent derivatives) as molecular building blocks of GNRs and, in parallel, several PORs (tetra- or di-substituted) with appropriate structural features to functionalize GNRs. Alternatively, POR-fused GNRs hybrid precursors will be synthesized via direct functionalization of PORs with GNRs precursors or via synthesis of GNRs precursors bearing aldehyde groups. Several polymerization strategies will be explored (“growing stages”), using in-solution synthesis (ISS) or on-surface synthesis (OSS), namely on Au(111) surfaces. The polymerization reactions will involve, for example, Suzuki or Ullmann coupling. Depending on the properties of the starting GNRs and POR precursors, the final structures may either be one- or two-dimensional (1D GNRs/PORs or 2D NPG/PORs, respectively). Finally, the successfully synthesized hybrid materials will be explored as gas sensors for future electronic devices. It is expected that the outcomes from GRAPHYRIN will allow to go beyond the state-of-the-art and take a step further towards the synthesis of new custom-made graphene/POR nanoarchitectures for ideal gas sensing electronic devices.