We describe the ligand directed self assembly of two mesoscopic supramolecular MOF architectures based upon the rigid ligand cis,trans-1,3,5-triaminocyclohexane with copper(II) salts. The use of copper fluoride results in the assembly of an unprecedented cubic 3D network with 1 nm void spaces while the use of copper sulfate yields a hexagonal 3D layered network containing nanotubes which are 1.5 nm in diameter. Further, experiments probing the self assembly of the structures after complexation using cryospray mass spectrometry show it is possible to follow the nucleation events that lead to the supramolecular MOFs, and this opens up a new avenue for the direct observation and control of the assembly of complex inorganic architectures.
