Cap for Copper(I) Ions! Metallosupramolecular Solid and Solution State Structures on the Basis of the Dynamic Tetrahedral [Cu(phenAr2)(py)2]+ Motif

The tetrahedral [Cu(phenAr(2))(py)(2)](+) coordination motif (phen =1,10-phenanthroline; py = pyridine) conceived on the basis of the HETPYP concept (heteroleptic pyridyl and phenanthroline metal complexes) is a versatile dynamic unit for constructing various heteroleptic metallosupramolecular pseudo-1D, 2D, and 3D structures, both in solution and the solid state. The 2,9-diaryl substituted phenanthroline (phenAr(2)) serves as a capping ligand for copper(I) ions, as its bulky nature prevents formation of the homoleptic complex [Cu(phenAr(2))(2)](+). Combination of the dynamic and concave metal ligand building block [Cu(phenAr(2))](+) with various pyridine (py) ligands, such as bi-, tri-, and tetrapyridines, opened the way to infinite 1D helicates, 2D networks, and discrete 3D hexanuclear cages, whereas spatial integration of both phenAr(2) and py units into a single ligand resulted in the formation of a Borromean-ring-type hexanuclear cage.