It is accepted that only three elements are ferromagnetic at room temperature, the transition metals iron, cobalt and nickel. The Stoner criterion explains why, for example, iron is ferromagnetic but manganese is not, even though both elements have an unfilled 3d shell and are adjacent in the periodic table: the product of the density of states with the exchange integral must be greater than unity for spontaneous ordering to emerge.1,2 Here, we demonstrate that it is possible to alter the electronic states of nonferromagnetic materials, such as diamagnetic copper and paramagnetic manganese, in 2 order to drive them ferromagnetic at room temperature. This remarkable effect is achieved via interfaces between metallic thin films and C 60 molecular layers. The emergent ferromagnetic state can exist over several layers of the metal before being quenched at large sample thicknesses by the material's bulk properties. While the induced magnetisation is easily measurable by magnetometry, low energy muon spin spectroscopy 3 provides insight into its magnetic distribution by studying the depolarisation process of low energy muons implanted in the sample. This technique indicates localized spin-ordered states at and close to the metallo-molecular interface.Density functional theory simulations suggest a mechanism based on magnetic hardening of the metal atoms due to electron transfer. 4,5 This opens a path for the exploitation of molecular coupling to design magnetic metamaterials using abundant, non-toxic elements such as organic semiconductors. Charge transfer at molecular interfaces can then be used to control spin polarisation or magnetisation, with far reaching consequences in the design of devices for electronic, power or computing applications. 6,7 Multifunctional materials with the spin degree of freedom such as multiferroics, magnetic semiconductors and molecular magnets have all aroused huge interest as potentially transformative components in quantum technologies. [8][9][10][11][12] Strategies used to bring magnetic ordering to these materials typically rely on the inclusion of magnetic transition metals, heavy elements with a large atomic moment or rare earths. In thin film structures, proximity effects and coupling at interfaces play an essential role. 13,14 This is especially the case for molecular spintronics, 15,16 where organic thin films grown on copper have demonstrated spin filtering. 17The organic magnetic coupling can propagate for long distances in systems such as nanoscale vortex-like configurations or nanoskyrmion lattices. 183We choose C 60 as a model molecule due to its structural simplicity and robustness as well as its high electron affinity. C 60 /transition metal complexes exhibit strong interfacial coupling between metal 3d z electrons and molecular π-bonded p electrons. The potential created by the mismatch of molecular and metal work functions leads to a partial filling of the interface states. [19][20][21] Other molecules with close electron affinity and the potential for 3d z /p coupling ...

Interactions between a single emitter and cavity provide the archetypical system for fundamental quantum electrodynamics. Here we show that a single molecule of Atto647 aligned using DNA origami interacts coherently with a sub-wavelength plasmonic nanocavity, approaching the cooperative regime even at room temperature. Power-dependent pulsed excitation reveals Rabi oscillations, arising from the coupling of the oscillating electric field between the ground and excited states. The observed single-molecule fluorescent emission is split into two modes resulting from anti-crossing with the plasmonic mode, indicating the molecule is strongly coupled to the cavity. The second-order correlation function of the photon emission statistics is found to be pump wavelength dependent, varying from g (2) (0) = 0.4 to 1.45, highlighting the influence of vibrational relaxation on the Jaynes-Cummings ladder. Our results show that cavity quantum electrodynamic effects can be observed in molecular systems at ambient conditions, opening significant potential for device applications.

Reproducible confinement of light on the nanoscale is essential for the ability to observe and control chemical reactions at the single-molecule level. Here we reliably form millions of identical nanocavities and show that the light can be further focused down to the subnanometer scale via the creation of picocavities, single-adatom protrusions with angstrom-level resolution. For the first time, we stabilize and analyze these cavities at room temperatures through high-speed surface-enhanced Raman spectroscopy on specifically selected molecular components, collecting and analyzing more than 2 million spectra. Data obtained on these picocavities allows us to deduce structural information on the nanoscale, showing that thiol binding to gold destabilizes the metal surface to optical irradiation. Nitrile moieties are found to stabilize picocavities by 10-fold against their disappearance, typically surviving for >1 s. Such constructs demonstrate the accessibility of single-molecule chemistry under ambient conditions.

Small numbers of surface-bound molecules are shown to behave as would be expected for optomechanical oscillators placed inside plasmonic nanocavities that support extreme confinement of optical fields. Pulsed Raman scattering reveals superlinear Stokes emission above a threshold, arising from the stimulated vibrational pumping of molecular bonds under pulsed excitation shorter than the phonon decay time, and agreeing with pulsed optomechanical quantum theory. Reaching the parametric instability (equivalent to a phonon laser or "phaser" regime) is, however, hindered by the motion of gold atoms and molecular reconfiguration at phonon occupations approaching unity. We show how this irreversible bond breaking can ultimately limit the exploitation of molecules as quantum-mechanical oscillators, but accesses optically driven chemistry.

Polarized optical dark-field spectroscopy is shown to be a versatile noninvasive probe of plasmonic structures that trap light to the nanoscale. Clear spectral polarization splittings are found to be directly related to the asymmetric morphology of nanocavities formed between faceted gold nanoparticles and an underlying gold substrate. Both experiment and simulation show the influence of geometry on the coupled system, with spectral shifts Δλ = 3 nm from single atoms. Analytical models allow us to identify the split resonances as transverse cavity modes, tightly confined to the nanogap. The direct correlation of resonance splitting with atomistic morphology allows mapping of subnanometre structures, which is crucial for progress in extreme nano-optics involving chemistry, nanophotonics, and quantum devices.