Red-NIR luminescent hybrid poly(methyl methacrylate) containing covalently linked octahedral rhenium metallic clusters.

The embedding of functional inorganic entities into polymer matrices has become an intense field of investigation in which the main challenges are to keep the added value of the inorganic entities while preventing their self-aggregation within the organic matrix. We present a simple way to obtain a homogeneous highly red-NIR luminescent hybrid copolymer that contains covalently bonded nanometric-sized {Re(6)} octahedral clusters. The [Re(6)Se(i)(8)(OH)(a)(6)](4-) cluster complexes are primarily functionalized in two steps with tert-butylpyridine (TBP) and methacrylic acid (MAC) to give neutral [Re(6)Se(8)(TBP)(4)(MAC)(2)] building blocks that are copolymerized with methyl methacrylate (MMA) either in solution or in bulk in the presence of azobisisobutyronitrile as an initiator. Several samples containing 0, 0.025, 0.05, and 0.1 wt % of functionalized {Re(6)} clusters were prepared. As the {Re(6)} cluster/MMA ratio is very low, the obtained copolymers keep the entire processability of pure poly(methyl methacrylate) (PMMA), as demonstrated by differential scanning calorimetry and thermogravimetric analysis. Voltammetric and luminescence studies also indicate that the intrinsic properties of the clusters are preserved within the polymer matrix. All the samples show a bright (emission quantum yield=0.07), broad, and structureless emission band, which extends from lambda=600 nm to more than lambda=950 nm, with the maximum wavelength centered around lambda(em)=710 nm either in solution or in the solid state. Moreover, the high stability of the incorporated inorganic phosphors prevents the material from photobleaching, and thus the luminescence properties are kept entirely even after nine months of ageing.