A monomer–dimer nanoswitch that mimics the working principle of the SARS-CoV 3CLpro enzyme controls copper-catalysed cyclopropanation

Abstract

A triangular framework with a terpyridine and shielded phenanthroline at its termini constitutes an open/close nanoswitch that is toggled by chemical inputs. In the presence of copper(I) ions, the open triangular framework (OPEN-I) firmly closes to a catalytically inactive heteroleptic [Cu(phen)(terpy)]⁺ complex (CLOSE). Reversible switching between CLOSE and OPEN-I states was demonstrated by successive addition and removal of Cu⁺. In contrast, after addition of iron(II) ions to the CLOSE state a bishomoleptic dimeric [Fe(terpy)₂]²⁺ complex is formed with the copper(I) ions placed in the phenanthroline cavities (OPEN-II). Due to its coordinatively unsaturated [Cu(Phen)]⁺ sites the dimeric iron complex is able to serve as a catalyst in the cyclopropanation of Z-cyclooctene using ethyl diazoacetate.