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

Informations projet

GRAPHYRIN

N° de convention de subvention: 101150002

DOI

10.3030/101150002

Projet clôturé

Date de signature de la CE 7 Mars 2024

Date de début 1 Juillet 2024

Date de fin 30 Juin 2026

Financé au titre de

• Marie Skłodowska-Curie Actions (MSCA)

Coût total

Aucune donnée

Contribution de l’UE

€ 181 152,96

Coordonné par

UNIVERSIDAD DE SANTIAGO DE COMPOSTELA
Spain

Periodic Reporting for period 1 - GRAPHYRIN (Development of bottom-up custom-functionalized graphene/porphyrin nanoarchitectures with atomic precision)

Période du rapport: 2024-07-01 au 2026-06-30

Résumé du contexte et des objectifs généraux du projet

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-, di- or mono-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.

Travail effectué depuis le début du projet jusqu’à la fin de la période considérée dans le rapport et principaux résultats atteints jusqu’à présent

The project focused on the design and synthesis of new porphyrin-based molecular systems intended for integration with graphene nanostructures to create advanced materials for future molecular electronic devices.
During the early stages of the project, significant efforts were devoted to developing new organic synthetic routes required to obtain the molecular building blocks originally proposed. This led to the design and synthesis of a series of novel porphyrin architectures with extended π-conjugation, opening new research directions beyond those initially envisaged.
For example, one of the main achievements of the project was the development of indenyl coupling as a new synthetic strategy for constructing π-conjugated porphyrin systems on-surface. This methodology enabled the preparation of previously inaccessible molecular architectures and represents a valuable addition to the toolbox available for the synthesis of functional organic materials. The newly synthesized compounds were comprehensively characterized using advanced spectroscopic and analytical techniques to confirm their structures and investigate their optical and electronic properties. A second main achievement was the development of a new family of chiral porphyrin dimers connected through an axially chiral bianthracene scaffold. These molecules combine the unique optical and electronic properties of porphyrins with axial chirality, providing attractive platforms for future studies in chiroptical materials, molecular electronics, and photonic applications.
Overall, GRAPHYRIN significantly advanced the understanding of functional π-conjugated porphyrin materials and provided new molecular design strategies that will support the future development of advanced nanomaterials for electronic, optoelectronic, and sensing applications.

Progrès au-delà de l’état des connaissances et impact potentiel prévu (y compris l’impact socio-économique et les conséquences sociétales plus larges du projet jusqu’à présent)

GRAPHYRIN has generated significant advances in the field of functional π-conjugated materials through the development of novel porphyrin architectures and innovative synthetic methodologies. The project delivered new fundamental knowledge and molecular platforms that extend beyond the current state of the art. The results generated during the fellowship were actively disseminated to the scientific community through two poster presentations and two oral communications at international conferences. In addition, the project contributed to research training through the supervision of two research projects, one carried out by an undergraduate student and the other by a MSc student. The scientific outcomes are also being prepared for publication in peer-reviewed journals.

A major outcome of the project was the synthesis of a new family of chiral porphyrin dimers linked through an axially chiral bianthracene scaffold. These molecules represent a new class of π-conjugated chiral systems with potential applications in chiroptical materials, molecular electronics, asymmetric photonics, and spin-selective technologies. Their modular design also provides a versatile platform for the future development of more complex functional architectures. Another key achievement was the establishment of indenyl coupling as a new synthetic strategy for porphyrin chemistry. This methodology enables the construction of extended π-conjugated porphyrin systems that are difficult or impossible to access using conventional approaches, thereby expanding the synthetic toolbox available for the preparation of advanced organic functional materials.

The results provide several opportunities for further uptake. Future research will focus on extending the new synthetic methodologies to larger conjugated systems, integrating the developed molecular platforms with graphene nanostructures, and evaluating their performance in molecular electronic and sensing devices. Additional studies on their chiroptical and photophysical properties are also expected to broaden their range of applications.

Overall, GRAPHYRIN has delivered innovative molecular systems, new synthetic methodologies, and fundamental knowledge that significantly advance the design of functional π-conjugated materials and will support future developments in molecular optoelectronics.