Metal Atom Clusters as Building Blocks for Multifunctional Proton-Conducting Materials: Theoretical and Experimental Characterization.

The search for new multifunctional materials displaying proton-conducting properties is of paramount necessity for the development of electrochromic devices and supercapacitors as well as for energy conversion and storage. In the present study, proton conductivity is reported for the first time in three molybdenum cluster-based materials: (H)4 [Mo6 Br6 S2 (OH)6 ]-12H2 O and (H)2 [Mo6 X8 (OH)6 ]-12H2 O (X = Cl, Br). We show that the self-assembling of the luminescent [Mo6 L8 i (OH)6 a ]2-/4- cluster units leads to both luminescence and proton conductivity (σ = 1.4 × 10-4 S·cm-1 in (H)2 [Mo6 Cl8 (OH)6 ]-12H2 O under wet conditions) in the three materials. The latter property results from the strong hydrogen-bond network that develops between the clusters and the water molecules and is magnified by the presence of protons that are statistically shared by apical hydroxyl groups between adjacent clusters. Their role in the proton conduction is highlighted at the molecular scale by ab initio molecular dynamics simulations that demonstrate that concerted proton transfers through the hydrogen-bond network are possible. Furthermore, thermogravimetric analysis also shows the ability of the compounds to accommodate more or less water molecules, which highlights that vehicular (or diffusion) transport probably occurs within the materials. An infrared fingerprint of the mobile protons is finally proposed based on both theoretical and experimental proofs. The present study relies on a synergic computational/experimental approach that can be extended to other proton-conducting materials. It thus paves the way to the design and understanding of new multifunctional proton-conducting materials displaying original and exciting properties.