The newly synthesised ligand 2 combines binding components known to un
dergo specific and distinct self-assembly processes with Cu-I ions, It
complexes Cu-I to form, in almost quantitative yield, a large inorgan
ic architecture 1 made up from four ligand molecules and twelve metal
ions. The structure of 1 was ascertained by X-ray radiocrystallography
as well as by NMR spectroscopy and electrospray mass spectrometry. It
consists of a macrocycle of nanometric dimension with an external dia
meter of 28 Angstrom; the central cavity has a diameter of 11 Angstrom
, which contains four PF6- anions as well as solvent molecules. The sp
ontaneous formation of 1 results from a self-assembly process based on
a ''program'' combining two assembly subroutines, each specific to on
e of the ligand subunits. Self-assembly through double or, more genera
lly, multiple subroutines can be used to generate a wide variety of hi
ghly complex inorganic supramolecular architectures by combination of
two or more assembly processes.