The design of artificial systems that mimic highly evolved and finely tuned natural photosynthetic is a subject intensive research. We report herein new approach to constructing supramolecular for the photocatalytic generation hydrogen from water by encapsulating an organic dye molecule into pocket redox-active metal–organic polyhedron. assembled neutral Co4L4 tetrahedron consists four ligands cobalt ions connect together in alternating fashion. are coordinated three thiosemicarbazone NS...

A multiple-photon photochemical process breaks the existing energy limitation of visible-light photocatalysis. Through careful incorporation both bis(3,5-dicarboxyphenyl)pyridine and bis(3,5-dicarboxyphenyl)methylpyridinium ligands into a single metal–organic framework (MOF), we report herein photocatalytic C–N C–C oxidative coupling reactions that evidenced direct two-photon response process. Time-dependent luminescence-decay studies demonstrated reached same excited state by absorption as...

Abstract Pd catalysts are widely used in alkynol semi-hydrogenation. However, due to the existence of scaling relationships adsorption energies between key adsorbed species, increase conversion is frequently accompanied by side reactions, thereby reducing selectivity alkenols. We report that simultaneous alkenol and achieved manipulating interstitial atoms including B, P, C, S N catalysts. A negative linear relationship observed activation entropies 2-methyl-3-butyn-2-ol...

Supramolecular catalysis is established to modify reaction kinetics by substrate encapsulation, but manipulating the thermodynamics of electron-transfer reactions remains unexplored. Herein, we reported a new microenvironment-shielding approach induce an anodic shift in redox potentials hydrazine substrates, reminiscent enzymatic activation for N–N bond cleavage within metal–organic capsule H1. Equipped with catalytic active cobalt sites and substrate-binding amide groups, H1 encapsulated...

Abstract Enzymes facilitate chemical conversions through the collective activity of aggregated components, but marriage aggregation‐induced emission (AIE) with molecular containers to emulate enzymatic conversion remains challenging. Herein, we report a new approach construct Pt II ‐based octahedral cage AIE characteristics for photocyclization alkynylaniline by restricting rotation pendant phenyl rings peripheral corner. With presence water, C−H⋅⋅⋅π interactions involving triphenylphosphine...

Abstract Modifying redox potential of substrates and intermediates to balance pairs steps are important stages for multistep photosynthesis but faced marked challenges. Through co‐clathration iridium photosensitizer imine substrate within one packet a metal‐organic capsule shift the potentials substrate, herein, we reported multiphoton enzymatic strategy generation heterocycles by intramolecular C−X hydrogen evolution cross‐couplings. The cage facilitated pre‐equilibrium substrate‐involving...

Abstract Solar production of hydrogen by consuming low‐value waste products is an attractive pathway that has both economic and environmental benefits. Inspired the reactive pocket enzymes, a synthetic platform to combine photocatalytic evolution with sulfide oxidation in one‐pot process via control over location electron‐transfer steps developed. The redox‐active coordination vessel Ni‐ TFT , which octahedral pocket, encapsulates organic dye pre‐organize for proton reduction oxidative...

Abstract Modifying the reactivity of substrates by encapsulation is essential for microenvironment catalysts. Herein, we report an alternative strategy that modifies entry behaviour reactants into and substrate inclusion thermodynamics related to capsule control electron injection kinetics selectivity products from nitroarenes photoreduction. The includes orchestration openings donors, capsule’s pocket encapsulate more than one nitroarene molecules, facilitating a condensation reaction...

Converting dilute CO2 source into value-added chemicals and fuels is a promising route to reduce fossil fuel consumption greenhouse gas emission, but integrating electrocatalysis with capture still faced marked challenges. Herein, we show that self-healing metal–organic macrocycle functionalized as an electrochemical catalyst selectively produce methane from flue air the lowest applied potential so far (0.06 V vs reversible hydrogen electrode, RHE) through enzymatic activation fashion. The...

A series of ladder chromophores featuring planar structures fused perylenebisimide and carbazole have been efficiently synthesized via photocyclization under sun light. Compared to N,N'-bis(3-pentyl) (PBI-1), they show remarkably enhanced nonlinear properties.

CuI-catalyzed oxidative reaction of amidines with C60 using air as the oxidant has been exploited for easy preparation fulleroimidazole derivatives. Furthermore, this kind [3 + 2] also successfully applied in synthesis fullerooxazole derivatives starting from amides first time. The substrate scope is broad, and process particularly cheap simple.

Triply interlocked metal organic catenanes with several kinds of individual pockets enabled the possibility encapsulating different anions, allowing dynamic allostery between unlocked/locked conformers to efficiently promote dehalogenation reaction.

The selective hydrogenation of pyridines containing reducible groups such as 2‐phenylpyridine typically has low yields due to strong nitrogen coordination with the metal well non‐selective and over‐hydrogenation. We report synthesis a novel Pd trimer catalyst through confined growth on an ordered mesoporous carrier, characterized by 0.42 d‐electron deficiency address this challenge. This achieved nearly complete conversion selectivity 2‐phenylpiperidine, maintaining its performance across 8...

The selective hydrogenation of pyridines containing reducible groups such as 2‐phenylpyridine typically has low yields due to strong nitrogen coordination with the metal well non‐selective and over‐hydrogenation. We report synthesis a novel Pd trimer catalyst through confined growth on an ordered mesoporous carrier, characterized by 0.42 d‐electron deficiency address this challenge. This achieved nearly complete conversion selectivity 2‐phenylpiperidine, maintaining its performance across 8...

Iridium photosensitizer encapsulated metal-organic cage was constructed for photocatalytic generation of heterocycles by intramolecular C-X (O, N, S) hydrogen evolution cross-couplings under mild conditions. The host-dye-substrate co-encapsulation approach enabled imine...

The Cu(OAc)2-mediated intermolecular diamination reaction of C60 with ureas allows the concise and efficient preparation fulleroimidazolidinones involving cleavage two N–H bonds formation C–N bonds. Both dialkylated diarylated can be synthesized using this method.

Mixed-ligand Zn-MIX was obtained for the photooxidation of amines and sulfides, which presents a promising strategy design multi-component MOFs with considerable photocatalytic activity.

The efficiency of photosensitization and hydrogen atom transfer (HAT) catalysis is balanced in a recyclable heterogeneous manner by the modification N-central conformation Cd-<bold>MIX</bold>.

Abstract Modifying redox potential of substrates and intermediates to balance pairs steps are important stages for multistep photosynthesis but faced marked challenges. Through co‐clathration iridium photosensitizer imine substrate within one packet a metal‐organic capsule shift the potentials substrate, herein, we reported multiphoton enzymatic strategy generation heterocycles by intramolecular C−X hydrogen evolution cross‐couplings. The cage facilitated pre‐equilibrium substrate‐involving...

Abstract An enzyme‐mimicking catalytic system has been established using a singular palladium‐based octahedral cage as the supramolecular reactor, deftly unlocking off‐on‐off selectivity in semi‐hydrogenation of alkynes. Water serves critical regulator, modulating catalyst states, reaction rates, and endpoints. The choice solvent influences activity host–guest binding types homogeneous heterogeneous catalysis, effectively modifying steps involved Z → E isomerization during Kinetic inhibition...