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Despite the proven ability to form supramolecular assemblies via coordination to copper halides, organometallic building blocks based on four-membered cyclo -P 4 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 Cp R Ta(CO) 2 (η 4 -P 4 ) ( 1a : Cp R = Cp''; 1b : Cp R = 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 6  - was investigated as to their self-assembly in the absence and in the presence of the template molecule P 3 Se 4 . The two-component self-assembly of the building block 1a and the coinage-metal salt AgSbF 6 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 P 3 Se 4 @[{(Cp''Ta(CO) 2 (η 4 -P 4 ))Ag} 8 ] 8+ of 2.49 nm in size was formed. Moreover, cyclo -P 4 -based supramolecules are connected in a 2D coordination network by dinitrile linkers. The obtained compounds were characterised by mass-spectrometry, 1 H and 31 P NMR spectroscopy and X-ray structure analysis.

Use of a cyclo-P4 building block – a way to networks of host–guest assemblies

Use of a cyclo-P₄ building block – a way to networks of host–guest assemblies