Use of a -P building block - a way to networks of host-guest assemblies.

Despite the proven ability to form supramolecular assemblies coordination to copper halides, organometallic building blocks based on four-membered -P ligands find only very rare application in supramolecular chemistry. To date, only three types of supramolecular aggregates were obtained based on the polyphosphorus end-deck complexes CpTa(CO)(η-P) (: Cp = Cp''; : Cp = Cp'''), with none of them, however, possessing a guest-accessible void. To achieve this target, the use of silver salts of the weakly coordinating anion SbF was investigated as to their self-assembly in the absence and in the presence of the template molecule PSe. The two-component self-assembly of the building block and the coinage-metal salt AgSbF leads to the formation of 1D or 3D coordination polymers. However, when the template-driven self-assembly was attempted in the presence of an aliphatic dinitrile, the unprecedented barrel-like supramolecular host-guest assembly PSe@[{(Cp''Ta(CO)(η-P))Ag}] of 2.49 nm in size was formed. Moreover, -P-based supramolecules are connected in a 2D coordination network by dinitrile linkers. The obtained compounds were characterised by mass-spectrometry, H and P NMR spectroscopy and X-ray structure analysis.