The heterometallic one-dimensional solvated coordination polymer [NiPtCl(TRIP-Py)].

The ditopic ligand 10-[4-(pyridin-4-yl)phenyl]-9-phospha-10-silatriptycene (TRIP-Py, CHNPSi) binds as a pyridine donor to Ni and as a phosphatriptycene donor towards Pt. The selectivity relies entirely on the Pearson character of the donor sites and the matching hardness of the respective metal cations. The product is the one-dimensional coordination polymer catena-poly[[[dichloridonickel(II)]-bis{μ-10-[4-(pyridin-4-yl)phenyl]-9-phospha-10-silatriptycene}-bis[dichloridoplatinum(II)]-bis{μ-10-[4-(pyridin-4-yl)phenyl]-9-phospha-10-silatriptycene}] dichloromethane pentasolvate ethanol icosasolvate], {[NiPtCl(TRIP-Py)]·5CHCl·20EtOH} (1), which retains large pores due to the inherent rigidity of the ligand.

A Rigid Linker for Site-Selective Coordination of Transition Metal Cations: Combining an Acetylacetone with a Caged Phosphine.

The combination of a soft phosphorus and a hard oxygen donor in the new ligand HacacTRIP leads to excellent site selectivity for the coordination of two different metal cations of matching Pearson character. The deprotonation step required for coordinating the acetylacetone oxygen donor further increases the selectivity. In contrast to most phosphines, the use of the caged phosphatriptycene motif enables a rigid and directional orientation of the phosphorus binding site which is required to form stable coordination network structures.

Phosphorus or nitrogen - the first phosphatriptycene in coordination polymer chemistry.

Phosphasilatriptycene, a phenylene spacer and a pyridyl moiety represent the building blocks of TRIP-Py, the first heteroditopic ligand featuring a phoshatriptycene scaffold. The P and N donor sites located at opposite ends of the prolate TRIP-Py molecule selectively coordinate metal cations matching their Pearson character. The harder pyridyl donor binds to Zn, the softer phosphorus donor to Pt, Hg and Au.