Deep red luminescent hybrid copolymer materials with high transition metal cluster content

Abstract

Accepted 04 Dec 2013International audienceThe hybrid strategy is a powerful approach to design functional materials by combining inorganic dyes with an organic matrix. However, introducing high contents of inorganic species within the hybrid material is a real challenge that requires a perfect balance between the interactions of both components to avoid mainly phase segregation problems. Based on our demonstration on an anionic molybdenum cluster, we present a general method to introduce high contents of such class of nanometre sized inorganic molecular deep red dyes in a polymer matrix. Our strategy exploits the physical interactions between the organic and inorganic parts of the hybrid material and allows a high cluster rate to be introduced (up to 50 wt%) in the polymer matrix. The resulting hybrids are remarkably stable even after several months of ageing. Moreover, the Mo clusters maintain their intrinsic deep red luminescence properties while the polymer organic matrix fully maintains its processability, thanks to the di-anionic character of the Mo6 clusters. Such materials show promising prospects in applications needing deep red emitters

From Cs2Mo6Cl14 to Cs2Mo6Cl14·H2O and Vice Versa: Crystal Chemistry Investigations

“…Face-capped Mo 6 X i 8 X a 6 units containing octahedral molybdenum clusters are the basic buildings blocks of many inorganic solid state compounds, hybrid frameworks and nanomaterials [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. Formation of Mo 6 cluster occurs at high temperatures via solid state reactions.…”

Syntheses, Structures, and Luminescence Properties of New Octahedral Cluster Complexes with Terminal Phenolate Ligands: [K(H2O)(CH3OH)3]2[Ph4P]2[M 6Cl12(O–C6H4–F)6] (M = Nb, Ta; Ph = phenyl)

“…They are the first hexanuclear niobium and tantalum cluster compounds showing luminescence properties. They might have high potential for photochemical applications [34][35][36][37][38].…”

One-pot synthesis of {Mo6 I8 }4+ -doped polystyrene microspheres via a free radical dispersion copolymerisation reaction

“…Doping of conventional polymers such as poly(methyl methacrylate), poly( N ‐vinylcarbazole), polystyrene (PS), polyurethane, etc., with phosphorescent hexanuclear octahedral cluster complexes [{M 6 X 8 }L 6 ] m (where M is Mo and X is Cl, Br or I; or M is Re and X is S or Se; and L is an apical ligand) has recently emerged as a simple and a convenient method to prepare new luminescent materials . These hybrid materials demonstrated potential both for materials‐based applications including fibrous materials for photonics and data transmission, polymer light‐emitting diodes and oxygen sensing and for biomedicine, e.g.…”

“…Among the whole family of hexanuclear metal clusters, octahedral molybdenum cluster complexes are at the moment the most thoroughly studied moieties due to their outstandingly high photoluminescence quantum yields that can be achieved by careful selection of inner and apical ligands . Several routes have been explored for incorporation of these cluster complexes into organic matrices including (i) co‐dissolution of metal clusters and polymers followed by solvent evaporation (often combined with processing into particles, films or fibres); (ii) free radical polymerisation of organic monomers with pre‐made cluster complexes featuring vinyl group functionality within their ligands or counter‐ions; and (iii) impregnation of cluster complexes, having labile apical ligands, into functionalised organic polymers . Notably, any of these procedures usually employ at least two steps, such as synthesis of a bespoke (functionalised) polymer; synthesis of a bespoke (functionalised) metal cluster; doping of polymer by cluster; and processing of the metal cluster/polymer hybrid.…”