PbP7 – a polyphosphide with a three-dimensional [P7]2− network of condensed and P-bridged P6 hexagons

摘要: The first lead polyphosphide PbP7 was synthesized from the elements in a flux through low-temperature route. structure determined single crystal X-ray diffractometer data: new type, P21/c, = 970.70(11), b 673.34(10), c 1243.89(18) pm, β 122.55(1)°, wR 0.0488, 2022 F2 values and 74 variables. exhibits pronounced three-dimensional phosphorus substructure that derives modification of black phosphorus: rows trans-edge-sharing P6 hexagons chair conformation are condensed via P bridges. Two seven crystallographically independent atoms have two five them three neighbours, leading to an electron-precise Zintl-like description Pb2+P−P−P0P0P0P0P0. P–P distances lie small range 219 225 indicating bond character. fill large cages left by phosphide substructure. Each atom is coordinated six (283–333 pm Pb–P) form half-shell (capped pentagon). opposite side claims space for lone pair (L) very long Pb–Pb 473 between adjacent P6PbL pairs. Consistent with structure, 31P magic-angle spinning (MAS) NMR spectra show distinct signal components equal peak areas.