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Superatomic crystals are composed of discrete modular clusters that emulate the role of atoms in traditional atomic solids$^{1-4}$. Owing to their unique hierarchical structures, these materials are promising candidates to host exotic phenomena, such as superconductivity and magnetism that can be revealed through doping$^{5-10}$. Low-dimensional superatomic crystals hold great promise as electronic components$^{11,12}$, enabling these properties to be applied to nanocircuits, but the impact of doping in such compounds remains unexplored. Here we report the electrical transport properties of Re$_6$Se$_8$Cl$_2$, a two-dimensional superatomic semiconductor$^{13,14}$. Using an in situ current annealing technique, we find that this compound can be n-doped through Cl dissociation, drastically altering the transport behaviour from semiconducting to metallic and giving rise to superconductivity below $\sim$ 9 K. This work is the first example of superconductivity in a van der Waals (vdW) superatomic crystal; more broadly, it establishes a new chemical strategy to manipulate the electronic properties of vdW materials with labile ligands.

Unconventional superconductivity typically occurs in materials in which a small change of a parameter such as bandwidth or doping leads to antiferromagnetic or Mott insulating phases. As such competing phases are approached, the properties of the superconductor often become increasingly exotic. For example, in organic superconductors and underdoped high-$T_\mathrm{c}$ cuprate superconductors a fluctuating superconducting state persists to temperatures significantly above $T_\mathrm{c}$. By studying alloys of quasi-two-dimensional organic molecular metals in the $\kappa$-(BEDT-TTF)$_2$X family, we reveal how the Nernst effect, a sensitive probe of superconducting phase fluctuations, evolves in the regime of extreme Mott criticality. We find strong evidence that, as the phase diagram is traversed through superconductivity towards the Mott state, the temperature scale for superconducting fluctuations increases dramatically, eventually approaching the temperature at which quasiparticles become identifiable at all., Comment: 19 pages, 4 figures, 1 table

We present a multi-frequency Electron Spin Resonance (ESR) study in the range of 4 GHz to 420 GHz of the quasi-one-dimensional, non-dimerized, quarter-filled Mott insulators, delta-(EDT-TTF-CONMe_2)_2X (X=AsF_6, Br). In the high temperature orthorhombic phase above T~190 K, the magnitude and the temperature dependence of the high temperature spin susceptibility are described by a S = 1/2 Heisenberg antiferromagnetic chain with J_AsF6=298 K and J_Br=474 K coupling constants for X=AsF_6 and Br respectively. We estimate from the temperature dependence of the line width an exchange anisotropy, J'/J of ~2 * 10^{-3}. The frequency dependence of the line width and the g-shift have an unusual quadratic dependence in all crystallographic orientations that we attribute to an antisymmetric exchange (Dzyaloshinskii--Moriya) interaction., Comment: 6 pages, 6 figures

An investigation of the P/T phase diagram of the quarter-filled organic conductors, [EDT-TTF-CONMe2]2X, is reported on the basis of transport and NMR studies of two members, X=AsF6 and Br of the family. The strongly insulating character of these materials in the low pressure regime has been attributed to a remarkably stable charge ordered state confirmed by 13C NMR and the only existence of 1/4 Umklapp e-e scattering favoring a charge ordering instead of the 1D Mott localization seen in (TM)2X which are quarter-filled compounds with dimerization. A non magnetic insulating phase instead of the spin density wave state is stabilized in the deconfined regime of the phase diagram. This sequence of phases observed under pressure may be considered as a generic behavior for 1/4-filled conductors with correlations.

In the two-dimensional organic charge-transfer salts kappa-(BEDT-TTF)2Cu[N(CN)2]Br{x}Cl{1-x} a systematic variation of the Br content from x = 0 to 0.9 allows us to tune the Mott transition by increasing the bandwidth. At temperatures below 50 K, an energy gap develops in the Cl-rich samples and grows to approximately 1000 cm-1 for T -> 0. With increasing Br concentration spectral weight shifts into the gap region and eventually fills it up completely. As the samples with x = 0.73, 0.85 and 0.9 become metallic at low temperatures, a Drude-like response develops due to the coherent quasiparticles. Here, the quasiparticle scattering rate shows a omega^2 dependence and the effective mass of the carriers is enhanced in agreement with the predictions for a Fermi liquid. These typical signatures of strong electron-electron interactions are more pronounced for compositions close to the critical value x_c \approx 0.7 where the metal-to-insulator transition occurs., Comment: 11 pages, 12 figures

Infrared reflection measurements of the half-filled two-dimensional organic conductors $\kappa$-(BEDT-TTF)$_2$Cu[N(CN)$_{2}$]Br$_{x}$Cl$_{1-x}$ were performed as a function of temperature ($5 {\rm K}