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Phosphine‐functionalized metal‐organic frameworks (P‐MOFs) as an emerging class of coordination polymers, have provided novel opportunities for the development of heterogeneous catalysts. Yet, compared with the ubiquitous phosphine systems in homogeneous catalysis, heterogenization of phosphines in MOFs is still at its early stage. In this Minireview, we summarize the synthetic strategies, characterization and catalytic reactions based on the P‐MOFs reported in literature. In particular, various catalytic reactions are discussed in detail in terms of phosphine ligand structure‐function relationship, including the potential obstacles for future development. Finally, we discuss the possible solutions, including new types of reactions and techniques as the perspectives for the development of P‐MOF catalysts, highlighting the opportunities and challenges. [ABSTRACT FROM AUTHOR]

Photo‐catalysis by small‐molecules is often limited by catalyst degradation and low electron‐transfer efficiency. Herein we report a stable N‐phenyl‐phenothiazine (PTH)‐derived porous coordination cage (PCC) as a highly efficient photocatalyst. By the incorporation of the photocatalytic PTH moiety into a PCC, aggregation‐induced quenching (AIQ) was shown to be reduced. An improvement in catalyst stability was discovered, ascribed to the synergistic effects of the PTH moieties. The catalyst, operating through a photolytic single‐electron transfer, was utilized for photo‐catalyzed dehalogenation and borylation. Evaluation of the catalytic mechanism in the borylation reaction showed that the improved performance results from the more efficient formation of the electron donor‐acceptor (EDA) complex with the cage. This discovery provides a potential strategy to improve the photophysical properties and stabilities of small‐molecule organic photocatalysts via supramolecular chemistry. [ABSTRACT FROM AUTHOR]

Precise shaping of metal–organic frameworks (MOFs) is significant in both fundamental coordination chemistry and practical applications, such as catalysis, separation, and biomedicine. Herein, we demonstrated a linker scissoring strategy for precisely shaping MOFs through surface conformational pairing. In this strategy, the bidentate linkers which were designed according to the original tetratopic ligands and the coordination environment of MOF surfaces, were utilized as the covering agents. The shape of these covering agents and the surface conformation of metals onto MOFs restricted them to coordinate on specific MOF facets thus precisely controlling the shape of the MOFs. Different shapes of PCN‐608 from nanoplate (PCN‐NP) to nanorod (PCN‐NR) have been targeted by adding different bidentate linkers. The universality of this strategy was demonstrated by controlling the shapes of the NU‐MOFs from nanoplate to nanorod. This strategy provides a new guiding principle to synthesize MOF nanocrystals with controlled shapes. [ABSTRACT FROM AUTHOR]

High‐efficiency photocatalysis in metal‐organic frameworks (MOF) and MOF nanosheets (NSs) are often limited by their short‐lived charge separation as well as self‐quenching. Here, we propose to use the energy‐transfer process (EnT) to increase charge separation, thus enhancing the catalytic performance of a series of MOF NSs. With the use of NS, the photocatalyst can also be well isolated to reduce self‐quenching. Tetrakis(4‐carboxyphenyl) porphyrin (H4TCPP) and 1,3,6,8‐tetrakis(p‐benzoic acid)pyrene (H4TBAPy) linkers were chosen as the acceptor and donor moieties, respectively. Accounting for the precise spatial design afforded by the MOF NSs, the donor and acceptor moieties could be closely positioned on the NSs, allowing for an efficient EnT process as well as a high degree of site isolation. Two templates, donor‐on‐acceptor NS and acceptor‐on‐donor NS catalysts, were successfully synthesized, and the results show that the second one has much enhanced catalytic performances over the first one due to site‐isolated active photocatalysts. [ABSTRACT FROM AUTHOR]

The poor electrical conductivity of two‐dimensional (2D) crystalline frameworks greatly limits their utilization in optoelectronics and sensor technology. Herein, we describe a conductive metallophthalocyanine‐based NiPc‐CoTAA framework with cobalt(II) tetraaza[14]annulene linkages. The high conjugation across the whole network combined with densely stacked metallophthalocyanine units endows this material with high electrical conductivity, which can be greatly enhanced by doping with iodine. The NiPc‐CoTAA framework was also fabricated as thin films with different thicknesses from 100 to 1000 nm by the steam‐assisted conversion method. These films enabled the detection of low‐concentration gases and exhibited remarkable sensitivity and stability. This study indicates the enormous potential of metallophthalocyanine‐based conductive frameworks in advanced stand‐off chemical sensors and provides a general strategy through tailor‐make molecular design to develop sensitive and stable chemical sensors for the detection of low‐concentration gases. [ABSTRACT FROM AUTHOR]

Abstract: The development of porous composite materials is of great significance for their potentially improved performance over those of individual components and extensive applications in separation, energy storage, and heterogeneous catalysis. Now mesoporous metal–organic frameworks (MOFs) with macroporous melamine foam (MF) have been integrated using a one‐pot process, generating a series of MOF/MF composite materials with preserved crystallinity, hierarchical porosity, and increased stability over that of melamine foam. The MOF nanocrystals were threaded by the melamine foam networks, resembling a ball‐and‐stick model overall. The resulting MOF/MF composite materials were employed as an effective heterogeneous catalyst for the epoxidation of cholesteryl esters. Combining the advantages of interpenetrative mesoporous and macroporous structures, the MOF/melamine foam composite has higher dispersibility and more accessibility of catalytic sites, exhibiting excellent catalytic performance. [ABSTRACT FROM AUTHOR]

Keywords: Design; Linker Scissoring; Metal-Organic Frameworks; Separation; Shaping EN Design Linker Scissoring Metal-Organic Frameworks Separation Shaping 1 1 1 09/07/22 20220912 NES 220912 B Eine "Linker-Scissoring"-Strategie b wird im Forschungsartikel (e202207786) von Hong-Cai Zhou, Zhi-Yuan Gu und Mitarbeitern vorgestellt, mit der die Form nanopartikulärer metallorganischer Gerüste (MOFs) von Nanoplättchen zu Nanostäbchen durch Oberflächenkonformationspaarung gesteuert werden kann. Design, Linker Scissoring, Metal-Organic Frameworks, Separation, Shaping Titelbild: Linker Scissoring Strategy Enables Precise Shaping of Metal-Organic Frameworks for Chromatographic Separation (Angew. [Extracted from the article]