A Barrel-Shaped Metal-Organic Blue-Box Analogue with Photo-/Redox-Switchable Behavior

Chemistry. 2020 Dec 9;26(69):16455-16462. doi: 10.1002/chem.202003073. Epub 2020 Oct 28.

Abstract

Donor-acceptor interactions are ubiquitous in the design and understanding of host-guest complexes. Despite their non-covalent nature, they can readily dictate the self-assembly of complex architectures. Here, a photo-/redox-switchable metal-organic nanocapsule is presented, which was assembled by using lanthanide ions and viologen building blocks, by relying on such donor-acceptor interactions. The potential of this unique barrel-shaped structure is highlighted for the encapsulation of suitable electron donors, akin to the well-investigated "blue-box" macrocycles. The light-triggered reduction of the viologen units has been investigated by single-crystal-to-single-crystal X-ray diffraction experiments, complemented by magnetic, optical, and solid-state electrochemical characterizations. Density functional theory (DFT) calculations were employed to suggest the most likely electron donor in the light-triggered reduction of the viologen-based ligand.

Keywords: lanthanides; nanocapsules; redox chemistry; stimuli-responsive; viologen.