Double Subroutine Self‐Assembly; Spontaneous Generation of a Nanocyclic Dodecanuclear Cu¹ Inorganic Architecture

The newly synthesised ligand 2 combines binding components known to undergo specific and distinct self‐assembly processes with Cu 1 ions. It complexes Cu 1 to form, in almost quantitative yield, a large inorganic 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 diameter of 28 Å; the central cavity has a diameter of 11 Å, which contains four PF − 6 anions as well as solvent molecules. The spontaneous formation of 1 results from a self‐assembly process based on a “program” combining two assembly subroutines, each specific to one of the ligand subunits. Self‐assembly through double or, more generally, multiple subroutines can be used to generate a wide variety of highly complex inorganic supramolecular architectures by combination of two or more assembly processes.