Zusammenfassung
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 (CpTa)-Ta-R(CO)(2)(eta(4)-P-4) (1a: Cp-R = Cp ''; 1b: ...
Zusammenfassung
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 (CpTa)-Ta-R(CO)(2)(eta(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 SbF6- was investigated as to their self-assembly in the absence and in the presence of the template molecule P3Se4. The two-component self-assembly of the building block 1a and the coinage-metal salt AgSbF6 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 P3Se4@[{(Cp '' Ta(CO)(2)(eta P-4(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, H-1 and P-31 NMR spectroscopy and X-ray structure analysis.
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