Long excited state lifetime of thermally activated delayed fluorescent photosensitizer integrated into Metal-organic framework enables efficient CO2 photoreduction

Molecular Catalysis of Energy Relevance in Metal–Organic Frameworks: From Higher Coordination Sphere to System Effects

“…Bie et al reported the synthesis of Spiro-Zn-MOF , a 3D framework consisting of the organic PS SATC (5,5′-(10 H ,10′ H -9,9′-spirobi­[acridine]-10,10′-diyl)­diisophthalic acid) and Zn 2+ -based SBUs. The linker is a donor/acceptor structure that displayed an excited state lifetime up to a microsecond, which was preserved also in the Spiro-Zn-MOF .…”

Donor–Acceptor Mixed-Naphthalene Diimide-Porphyrin MOF for Boosting Photocatalytic Oxidative Coupling of Amines

“…As a category of newly emerged crystalline porous materials, metal–organic frameworks (MOFs) have been proposed as potential photocatalysts for selective oxidation reactions because of their unique excitation and charge transition mechanisms. − Recently, some MOFs have been reported for the photocatalytic aerobic oxidative coupling of amines, − but the reaction kinetics caused by the low efficiency of the photogenerated charge separation still needs to be greatly improved to meet the potential practical application requirements. There are many reported strategies in optimizing the photocatalytic activities of MOFs, in which the electron/energy transfer representing the central science of natural photosynthesis is widely introduced. − Assembling electron donor and acceptor chromophores in a single MOF can realize the photoinduced electron transfer (PET). − However, due to the construction of MOFs, in which donor and acceptor chromophores with similar geometry and connectivity both as ligands, is a great challenge, most of the current reported MOFs with the PET process are organized via using either the donor or the acceptor as the guest molecule, − which damages the porosities of MOFs and severely limits their applications in photocatalysis.…”

Mesoporous Mixed-Metal–Organic Framework Incorporating a [Ru(Phen)3]2+ Photosensitizer for Highly Efficient Aerobic Photocatalytic Oxidative Coupling of Amines

“…The development and full use of clean energy have been an essential research focus in recent decades. − Among many clean energy sources, sunlight is considered one of the best natural sources, and the organic transformation driven by visible light has successfully converted solar energy into chemical energy. − Under visible light irradiation with sufficiently high energy, a series of photoactivated chemical reactions could occur accompanied by the initiation of complex free radical mechanisms, so photocatalysis is widely viewed as a route to the green synthesis of some chemicals due to its environmental friendliness and high sustainability. − As the critical component of photocatalysis, a variety of materials have been explored and researched to induce electron–hole separation and promote photocatalytic organic transformation. However, the most efficient and practical visible-light-driven photocatalysts are still based mainly on the soluble complexes of noble metals with strong light absorption, such as Ru and Ir. − Several strategies for the utilization of the noble metal-based photocatalysts, including designing novel Ru/Ir complex-based molecular photosensitizers via the change of the ligand structure, loading small molecular photosensitizers onto different solid materials via electric adsorption, doping or deposition, and post-modifying metal ions on the skeleton of porous materials by coordination, have been developed. ,− Yet many unavoidable problems have to be faced on account of nonrecoverability, nonrecyclability, and scarcity for some expensive homogeneous photocatalysts, but poor interface contacts between phases, inefficient charge separation and transportation, uncontrollable load capacity, and deleterious semiconductor degradation side reactions for some heterogeneous photocatalysts. − Moreover, most reported photocatalysts can only be used for a specific reaction rather than the multireaction platform. − Therefore, it remains a huge challenge to develop efficient, recyclable, stable, and versatile photocatalysts nowadays.…”