Synthesis and Self‐Assembly of a Rigid Exotopic Bisphenanthroline Macrocycle: Surface Patterning and a Supramolecular Nanobasket

Abstract
The synthesis and characterisation of a rigid nanoscale macrocycle with two exotopic phenanthroline binding sites is reported. Scanning tunnelling microscopy (STM) at the solid–liquid interface reveals the formation of highly ordered monolayers of macrocycles with dimensions that are in good agreement with the calculated structure. Using the HETPHEN concept several bisheteroleptic coordination complexes with other phenanthrolines and a nanoscale basket assembly were prepared in presence of copper(I) ions. NMR spectroscopy, mass spectrometric data and elemental analysis point to three distinct isomers of the basket assembly in solution. A silver basket was prepared and readily converted to its copper analogue. Electrospray ionisation (ESI)‐MS and spectrophotometric investigations provided additional mechanistic insight into the assembly process. Hence, the exotopic bisphenanthroline macrocycle in combination with HETPHEN concept proves to be very effective in controlling the compositional aspects of multicomponent self‐assembly.