The Redox Coupling Effect in a Photocatalytic Ru^II‐Pd^II Cage with TTF Guest as Electron Relay Mediator for Visible‐Light Hydrogen‐Evolving Promotion

Abstract

Abstract A nanocage coupling effect from a redox Ru II ‐Pd II metal–organic cage (MOC‐16) is demonstrated for efficient photochemical H 2 production by virtue of redox–guest modulation of the photo‐induced electron transfer (PET) process. Through coupling with photoredox cycle of MOC‐16, tetrathiafulvalene (TTF) guests act as electron relay mediator to improve the overall electron transfer efficiency in the host–guest system in a long‐time scale, leading to significant promotion of visible‐light driven H 2 evolution. By contrast, the presence of larger TTF‐derivatives in bulk solution without host–guest interactions results in interference with PET process of MOC‐16, leading to inefficient H 2 evolution. Such interaction provides an example to understand the interplay between the redox‐active nanocage and guest for optimization of redox events and photocatalytic activities in a confined chemical nanoenvironment.