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

An anocage coupling effect from ar edoxR u II -Pd II metal-organic cage 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 relaym ediator to improve the overall electron transfer efficiency in the hostguest system in al ong-time scale,l eading 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. Suchi nteraction provides an example to understand the interplay between the redox-active nanocage and guest for optimization of redox events and photocatalytic activities in ac onfined chemical nanoenvironment.

A Robust Photocatalytic Hybrid Material Composed of Metal‐Organic Cages and TiO2 for Efficient Visible‐Light‐Driven Hydrogen Evolution

“…Inspired by the natural enzymes with ingenious structures, metal‐organic cages (MOCs) constructed with multiple redox‐active metal cation centers and coordinated connected optical‐active ligands have been developed due to their well‐defined shapes, specific cavities, nanoscale sizes and symmetrical geometries, which provide a good foundation for artificial photosynthesis. For such photosensitive MOCs, the effective and directional electron transfer from the light‐harvesting ligands to the catalytic metal centers makes them become promising intramolecular photochemical molecular devices (IPMDs), which have been applied in various photocatalytic reactions [17–20] …”

Interfacial Microenvironment Modulation Boosting Electron Transfer between Metal Nanoparticles and MOFs for Enhanced Photocatalysis

“…As a control, Fc@UiO‐66‐NH 2 cannot generate H 2 , hinting Pt is active site. In sharp contrast, when Fc is directly decorated on the external surface of Pt@UiO‐66‐NH 2 , the obtained Pt@UiO‐66‐NH 2 /Fc could well retain MOF structure (Figure S16), and presents much reduced H 2 production rate (102.6 μmol g −1 h −1 ), which might be ascribed to the steric hindrance of Fc preventing its encapsulation within UiO‐66‐NH 2 and the electron transfer from the MOF mainly to Fc instead of Pt [15] . The role of Fc in the photocatalytic H 2 production reaction is further decoded by in situ electron spin resonance (ESR).…”

Combining a Titanium–Organic Cage and a Hydrogen‐Bonded Organic Cage for Highly Effective Third‐Order Nonlinear Optics

“…As a new type of molecular containers, MOCs and HOCs have diverse applications in molecule recognition and separation, drug delivery and catalysis [23–28] . However, their applications in third‐order nonlinear optical (NLO) field are rarely explored to date [29] .…”

“…As a new type of molecular containers, MOCs and HOCs have diverse applications in molecule recognition and separation, drug delivery and catalysis. [23][24][25][26][27][28] However, their applications in third-order nonlinear optical (NLO) field are rarely explored to date. [29] On the other hand, the third-order NLO materials have been receiving intensive research interest in recent years because of their potential applications in optical limiting, optical switching, image transmission, logic devices and mode-locked laser system, and so on.…”