Replacing pure inorganic materials by functional organic-inorganic hybrid ones to lower production costs has become a major challenge, in particular for the optoelectronic industry. Adding nanostructuration abilities meanwhile preserving homogeneity is even more challenging for this class of new materials. Here we show that red-NIR emissive ternary molybdenum cluster salts can be assembled to liquid crystalline 15C5 crown ethers. The resulting hybrids are homogeneous and stable up to high temperature despite the weakness of the supramolecular interactions binding both components. These are illustrated by Cs MAS NMR. All hybrids show hexagonal columnar arrangements and strong red-NIR emission. Surprisingly, when chlorinated clusters are used instead of brominated ones, the mesophase stability is largely enhanced.

Crown ethers and their derivatives are versatile building blocks for the design of supramolecular materials. They can be functionalized at will and are well known for their abilities to complex with alkali cations. Here, we show that emissive lanthanide free hybrid materials can be generated by using such building blocks. The organic tribenzo[18]crown-6 central core was functionalized via six-fold Suzuki cross-coupling as a key reaction with three o-terphenyl units which could be converted into their corresponding triphenylenes by the Scholl reaction, leading to novel liquid-crystalline columnar materials. Selected tribenzo[18]crown-6 o-terphenyls could interact with emissive ternary metal cluster compound salts to generate hybrid materials combining the properties of both moieties. Due to synergistic effects and despite the anisometry of the cluster compounds, individual properties such as liquid-crystalline phase stability of the organic part and emission abilities of its inorganic counter-part are enhanced in the hybrid compounds.

Transition metal nitrides (TMN) form a class of materials with unique physical and chemical properties. Among them, molybdenum nitrides are mainly used as high-performance magnets or catalysts for a wide range of reactions. This work aims at developing innovative syntheses to prepare nanostructured TMN from metallic clusters for heterogeneous catalysis. The use of a nanoscale precursor such as (TBA)2Mo6Br14 (TBA = tetrabutylammonium = (C4H9)4N +) enables to reach different molybdenum nitride compositions (Mo2N, Mo5N6) by thermal reaction under ammonia at relatively low temperatures. Such a novel synthetic approach highlights the prime importance of the starting material to stabilize specific stoichiometries. The impact of this new synthetic route is characterized by several techniques including electron probe microanalysis and high-resolution transmission microscopy. Moreover, catalytic properties of these potential cost-effective catalysts are investigated for the Water-Gas Shift Reaction.