Solids chalcogenolates

The use of both di- or triphosphines and chalcogenolates as building blocks in the same molecule leads to different species. The trinuclear derivative shown in Figure 2.35 is an example [167]. A more complicated structure is that of Au9(p.-p-tc)6(p.-dppm)4]3+ (p-tc = p-thiocresolate) which exhibits short gold-gold interactions. An emission at 540 nm is observed upon excitation at 450 nm in the solid state at room temperature that increases in intensity at 77 [168]. 

Reports that thermolysis of metal chalcogenolate complexes offers a low-temperature route to the synthesis of novel solid state materials (32) is also stimulating research in this area. As is the case with copper(I) thiolates, lithium thiolates are often aggregated species (Section III.C) and from the few magnesium thiolate structures known (Section III.D) one sees a preference for monomeric and dimeric formulations when bulky substituents are present. 

Molecular thermolysis is a well-established approach to materials synthesis, offering the advantage of exceptionally low reaction temperatures that are usefiil either in the synthesis of metastable solids or in the fabrication of layered materials where atomic diffusion is not desirable. Chalcogenolate compounds have been used for decades as low-temperature sources of solid-state chalcogenido materials. With Ln, the earliest thermolysis investigation outlined... 

Finally, chalcogenolate compounds have also been used to deliver lattices with more electronegative anions, reflecting the relative instability of Ln ions bound only to chalcogenides. Solid-state LnN forms via the thermolysis of azobenzene compounds (Reaction 19). Similarly, in the thermolysis of Ln(SC6F5)3, fluoride abstraction leads to... 

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