Dicopper(II) metallacyclophanes with photoswitchable oligoacene spacers: a joint experimental and computational study on molecular magnetic photoswitches

Abstract

Dinuclear copper(II) complexes of the metallacyclophane-type, (nBu4N)4[Cu2(2,6-anba)2] (1) and (nBu4N)4[Cu2(1,5-naba)2]·4H2O (2) with photoactive 2,6-anthracene-(2,6-anba) and 1,5-naphthalenebis(oxamate) (1,5-naba) bridging ligands, are reported. They undergo a thermally reversible, solid-state photomagnetic (ON/OFF) switching between the moderately strong antiferromagnetically coupled dicopper(II) species and the corresponding magnetically uncoupled [4+4] photocycloaddition product. Density functional calculations give further insights on the intramolecular (“pseudo-bimolecular”) photocycloaddition reaction of the two facing 2,6-anthracene or 1,5-naphthalene spacers in this novel family of dicopper(II) oligoacenophanes. The unique ability of oligoacenes as photoswitchable antiferromagnetic wires between two CuII ions separated by relatively long intermetallic distances could be the basis for the development of new kinds of molecular spintronic devices, referred to as molecular magnetic switches.