Supramolecular engineering of multifunctional systems and devices: the molecular approach to 2D materials

Project Information

SUPRA2DMAT

Grant agreement ID: 833707

DOI

10.3030/833707

Project closed

EC signature date 6 May 2019

Start date 1 September 2019

End date 31 August 2024

Funded under

• EXCELLENT SCIENCE - European Research Council (ERC)

Total cost

€ 2 500 000,00

EU contribution

€ 2 500 000,00

Coordinated by

CENTRE INTERNATIONAL DE RECHERCHE AUX FRONTIERES DE LA CHIMIE FONDATION
France

Periodic Reporting for period 4 - SUPRA2DMAT (Supramolecular engineering of multifunctional systems and devices: the molecular approach to 2D materials)

Reporting period: 2024-03-01 to 2024-08-31

Summary of the context and overall objectives of the project

SUPRA2DMAT has been a cross-disciplinary project targeted at mastering principles of materials engineering, by using supramolecular strategies, to combine the extraordinary physical and chemical properties of graphene and other two-dimensional (2D) layered materials (2DLMs) with the chemical and functional programmability of molecular components, with the ultimate goal of tuning and boosting the properties of 2DLMs and conferring them a stimuli responsive nature. The monolayer nature of 2DLMs makes them highly sensitive to environmental changes at the nanoscale. Controlled processing and interfacing of 2DLMs with functional molecular assemblies were achieved by exploiting non-covalent and (dynamic) covalent chemistry approaches. The physisorption of redox, magnetic, or optical switches to generate crystalline superlattices on 2DLMs made it possible to fabricate high-performance electrical devices capable to simultaneously respond to more than two external independent stimuli. Structurally precise hairy 2D and three-dimensional (3D) layer-by-layer porous composites for multianalyte chemical sensing were tailored via chemisorption of supramolecular receptors of the target analyte onto the 2DLMs. Highest sensitivity and selectivity in the sensing of water molecules (humidity) as well as heavy or alkali metal ions through an electrical readout were guaranteed by the choice of the receptor and 2DLM and their nanostructuration.
The learnings achieved within SUPRA2DMAT enabled the emergence of a conceptually new generation of multifunctional high-performance devices for applications in optoelectronics and chemical sensing, and on the long term also in energy and spintronics. SUPRA2DMAT also brought a useful contribution to the development of future emerging technologies based on 2DLMs for light-weight, low-cost, and large-area applications products on flexible substrates, e.g. for nanoscale multifunctional logic technologies and environmental monitoring, thus opening new and important perspectives in materials science and nanoscience.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

The work performed and the main results achieved in SUPRA2DMAT include:
• Mastering the supramolecular approach relying both on chemisorption and physisorption to fully exploit the capacity of functional molecular assemblies to modulate and enhance the properties of 2DLMs when interfaced.
• Exploiting conventional and dynamic covalent chemistry (DCC), i.e. operating under thermodynamic control, to functionalize 2DLMs to generate highly ordered “hairy-2D” or robust 3D functional composites with controlled chemical composition and architecture, as key components for optoelectronics and sensing.
• Covalently decorating 2DLMs with ad hoc receptors of water molecules, mono- and bivalent ions, and heavy metals to exploit principles of molecular recognition to fabricate ultrasensitive, ultrafast, fully reversible, and highly selective sensors for environmental and potentially also health monitoring.
• Proposing universal protocols based on the combination of graphene and other 2DLMs with organic components capable to simultaneously respond to at least two external independent stimuli (redox, magnetic, electrical, or optical) to realize high-performance multifunctional optoelectronic devices.

The dissemination, communication, and public engagement activities are summarized as follows:
• >70 original scientific publications, including research articles and review articles, in international high-impact peer-reviewed journals (average impact factor (IF) >15), including 1 Chemical Reviews (IF: 51.4) 1 Chemical Society Reviews (IF: 40.4) 1 Nature Nanotechnology (IF: 38.1) 11 Advanced Materials (IF: 27.4) 8 Advanced Functional Materials (IF: 18.5) 1 Accounts of Chemical Research (IF: 16.4) 1 Angewandte Chemie International Edition (IF: 16.1) 3 ACS Nano (IF: 15.8) 4 Nature Communications (IF: 14.7) 2 Journal of the American Chemical Society (IF: 14.4) 2 Advanced Science (IF: 14.3) 6 Small (IF: 13), 1 Materials Horizons (IF: 12.2) Science Advances (IF: 11.7) Small Science (IF: 11.1) etc.
• 8 cover pages of prestigious scientific journals, including Chemical Reviews (1 front cover), Advanced Materials (1 front and 2 back covers), Advanced Functional Materials (2 back covers), Chemical Science (1 front cover), and ACS Applied Materials & Interfaces (1 front cover).
• >1,700 citations (source: Google Scholar).
• >30 press releases and research highlights in various institutional and science news media, such as AlphaGalileo, AZoMaterials, Bioengineer.org ChemistryViews, CIRFC, CNRS, CNRS Alsace, EurekAlert!, Graphene Flagship, IRIS Adlershof, ISIS, Nanowerk, Nature Research Device & Materials Engineering Community, Phys.org ScienceDaily, Scienmag, UNISTRA, etc.
• >50 invited/keynote/plenary talks and lectures in national and international conferences, schools, and workshops, >40 invited seminars in academic institutions.
• >100 social media posts, > 2,500 followers on X, >1,400 followers on Instagram.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

SUPRA2DMAT exploited materials engineering by mastering supramolecular approaches to combine the outstanding physical and chemical properties of graphene and other 2DLMs with the chemical and functional programmability of molecular components, with the ultimate goal of modulating and enhancing the properties of 2DLMs and imparting them a responsive nature. This was accomplished by unravelling the architecture vs. function relationship in hybrids structures of 2DLMs and molecular assemblies to attain a deep understanding and control over four most critical properties for radically improved performance and reliability for real-life applications. These strategies led to the engineering of a conceptually new generation of printable devices for optoelectronics and sensing applications, and brought a useful contribution to the development of future emerging technologies based on 2DLMs for light-weight, low-cost, and large-area applications products on flexible substrates. The knowledge developed in SUPRA2DMAT is also instrumental for future applications in energy and spintronics. In a broader context, SUPRA2DMAT offered novel solutions to nanoscale multifunctional logic applications and environmental monitoring, therefore opening novel and important perspectives in materials science and nanoscience.

Crosslinking MoS2 with benzenedithiols yielding percolation paths for charge transport.