Polymer/salt complexes lanthanides

Polymer-salt complexes involving the tripositive lanthanides have been investigated from the standpoint of conductivity, which is observed to be very low. In addition, the neutral complex Nd(DMP)3 (DMP = 2,2,6,6-tetraethyl,-3,5-heptane dionate) will dissolve in PEO although not electrically conductive this polymer may have utility as a laser material. To... 

This section describes systems which are at the border of what has been defined as being the scope of this review and therefore does not pretend to be comprehensive. Indeed, if there is a wealth of strictly inorganic materials and glasses into which NIR-crnitting lanthanide ions have been incorporated and which are clearly excluded from the review, there also exist a continuum between these materials and molecular entities, for instance coordination polymers and clusters which have been described in the two preceding sections. In continuity with these concepts are micro- and mesoporous materials into which lanthanide salts or complexes can be incorporated or attached. These are essentially zeolites and sol-gel materials, either conventional or the so-called inorganic-organic hybrids, as well as polymers. 

A simpler but equally effective approach has been employed by Ward and coworkers [25] in the preparation of coordination polymers using luminescent anionic complexes. Here transition metals with emissive MLCT states act as effective sensMsers for lanthanide emission in the NIR [25]. In this case cyanide groups were used as bridging units starting from stable Ru " complexes and simple Ln salts. Examples include [Ru(Bipy)(CN)4] [26,27], [Ru(Phen) (CN)4] - [28], [Ru(Bpym)(CN)4] -, [Ru(CN)4]2([i-Bpym) 4- [29], [Ru(Hat)(CN)4] - [25], [Ru(CN)4]3(p"-Hat) -, [ Ru(CN)4 2([i -Hat)]4-, [Cr(CN)6]"-, and [Co(CN)6] - [30]. The advantage of this method is that the building blocks are already kinetically stable in solution and the solid structure is dictated by the coordination number adopted by the lanthanide ion (Fig. 9.5). 

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