An M₂L₄ Molecular Capsule with a Redox Switchable Polyradical Shell

Abstract

Preparation of molecular nanostructures with polyradical frameworks remains a significant challenge because of the limited synthetic accessibility which is entirely different from that of neutral and ionic ones. Herein we report the quantitative formation of a new M L molecular capsule from metal ions and dihydrophenazine-based ligands. The capsule has a spherical nanocavity (ca. 1 nm in diameter) enclosed by eight redox-active, dihydrophenazine panels. Electrochemical oxidation of the capsule leads to the generation of multiple radical cations on the shell framework. Moreover, a stable tetra(radical cation) capsule can be reversibly obtained by chemical as well as electrochemical oxidation.

The Redox Coupling Effect in a Photocatalytic RuII‐PdII Cage with TTF Guest as Electron Relay Mediator for Visible‐Light Hydrogen‐Evolving Promotion

“…Along this line,synthetic strategies have been reported to engineer functional coordination innerspace of nanocages via incorporation of either redox-active or photoactive centers, [31][32][33][34] thus generating MOC-based photocatalytic hostguest systems to imitate natural photosynthesis, [9,[35][36][37][38][39] where the spatially separated electron and/or energy transfer processes can facilitate photocatalytic water/H 2 Ss plitting, as well as other chemical transformations.T oa chieve efficient conversion from solar energy to chemical energy in such hostguest systems,one of the fundamental factors is to control the photo-induced redox events in the confined chemical nanospace. [39,40] So far, many research efforts have been devoted to the exploration of electron and energy transfer processes between host and guest molecules,e ither depending on construction of photoactive hosts or resorting to encapsulation of dye guests,r espectively.…”

Coordination-driven Nanostructures with Polyaromatic Shells

“…The obtained polyaromatic cages and capsules display wide-ranging host capabilities, selective recognition and separation of substrates, unusual fluorescent properties, and remarkable stabilization of reactive species in solution, which have not been achieved by pervious nanostructures composed of small aromatic rings and/or π-conjugated wire-like units. Further incorporation of various polyaromatic panels, e.g., bearing cationic, 23 redox, 24 chromic, and magnetic properties, into coordination-driven nanostructures would create advanced supramolecular materials with unique functions.…”

The Redox Coupling Effect in a Photocatalytic RuII‐PdII Cage with TTF Guest as Electron Relay Mediator for Visible‐Light Hydrogen‐Evolving Promotion

“…Along this line, synthetic strategies have been reported to engineer functional coordination innerspace of nanocages via incorporation of either redox‐active or photoactive centers, thus generating MOC‐based photocatalytic host–guest systems to imitate natural photosynthesis, where the spatially separated electron and/or energy transfer processes can facilitate photocatalytic water/H 2 S splitting, as well as other chemical transformations. To achieve efficient conversion from solar energy to chemical energy in such host–guest systems, one of the fundamental factors is to control the photo‐induced redox events in the confined chemical nanospace .…”