Addressing single-molecule magnets via 1D nanoframeworks – SMM1D

Wider research context / theoretical framework:

One of the challenges in the field of molecular magnetism is to make single-molecule magnets (SMMs) practically controllable and accessible. The proposed project aims at controlled and addressable molecular magnetism by confining SMMs into 1D nanostructures, such as metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), conducting polymers and single-wall carbon nanotubes (SWCNTs).

Hypotheses / research questions / objectives:

Our main objective is to address SMMs via the 1D host. To this end, impacts of 1D nano confinements on molecular magnetism must be understood. Unique molecular arrangements can be achieved and coordination reactions can be directional inside crystalline 1D pores. Altered single-ion anisotropy, ligand field, and zero-field splitting, as well as host-guest interactions e.g. charge transfer, orbital hybridization, Förster resonance energy transfer (FRET), can lead to advanced magnetism e.g. metamagnetism, single-molecule magnetism at higher temperatures and in lower magnetic fields
Electrical addressing of SMMs can be achieved by measuring magnetoconductance through electrically conductive hosts.
Magneto-optical responses in UV-Vis absorption, Raman and fluorescence are expected to change substantially as SMMs undergo metamagnetic transitions.

Approach / methods:

We will encapsulate SMMs in crystalline MOFs, COFs and aligned SWCNTs, or coordination polymers. The magnetic properties will be comprehensively studied using bulk magnetometry, magneto-optical spectroscopy, core-level spectroscopy e.g. X-ray magnetic circular dichroism (XMCD), neutron scattering and single-spin microscopy. Magneto-transport will be sought in SMMs in electrically conductive hosts.

Level of originality / innovation:

“Designer molecular packing and interfaces” will be achieved by encapsulation of SMMs or synthesis of SMMs inside the 1D hosts of various optical and electrical properties. The controlled host-guest interactions offer means of optical and electrical addressing of SMMs.

Primary researchers involved:

The Austrian team (H. Shiozawa and T. Pichler, University of Vienna) is an expert in synthesis of coordination polymers and MOFs, CNTs and studies of their physical properties using electron spectroscopy (XPS, UPS and XAS) and microscopy (TEM, SEM), XMCD and bulk magnetometry.
French partner 1 (L. Alvarez, J-L Bantignies, N. Izard, R. Aznar, P. Dieudonne-George and V. Jacques, Laboratoire Charles Coulomb) has a strong expertise in molecule encapsulation into CNTs, magnetic field imaging, optical spectroscopy and X-ray and neutron crystallography.
Partner 2 (B. Jousselme and S. Campidelli, LICSEN, CEA- Saclay) is a group of leading chemists with expertise in the functionalization of CNT, graphene, supramolecular, macromolecular chemistry.
Partner 3 (P. Hermet, Institute Charles Gerhardt of Montpellier) is an expert in density-functional theory.