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Increasing the chemical complexity of metal–organic cages (MOCs) or polyhedra (MOPs) demands control over the simultaneous organization of diverse organic linkers and metal ions into discrete caged structures. Herein, we show that a pre-assembled complex of the archetypical cuboctahedral MOP can be used as a template to replicate such caged structure, one having a "triblock Janus-type" configuration that is both heterometallic and heteroleptic. [ABSTRACT FROM AUTHOR]

We have synthesised and characterised the two possible isomers of heteroleptic trigonal antiprismatic M12L6L′6 MOPs by screening reactions of rhodium acetate with different pairs of complementary dicarboxylate linkers. The resulting 12 new MOPs (eight of isomer A + four of isomer B) are microporous in the solid state, exhibiting Brunauer–Emmett–Teller (BET) surface areas as high as 770 m2 g−1. [ABSTRACT FROM AUTHOR]

Bond breaking is an essential process in chemical transformations and the ability of researchers to strategically dictate which bonds in a given system will be broken translates to greater synthetic control. Here, we report extending the concept of selective bond breaking to reticular materials in a new synthetic approach that we call Clip‐off Chemistry. We show that bond‐breaking in these structures can be controlled at the molecular level; is periodic, quantitative, and selective; is effective in reactions performed in either solid or liquid phases; and can occur in a single‐crystal‐to‐single‐crystal fashion involving the entire bulk precursor sample. We validate Clip‐off Chemistry by synthesizing two topologically distinct 3D metal‐organic frameworks (MOFs) from two reported 3D MOFs, and a metal‐organic macrocycle from metal‐organic polyhedra (MOP). Clip‐off Chemistry opens the door to the programmed disassembly of reticular materials and thus to the design and synthesis of new molecules and materials. [ABSTRACT FROM AUTHOR]

Use of preformed metal‐organic polyhedra (MOPs) as supermolecular building blocks (SBBs) for the synthesis of metal‐organic frameworks (MOFs) remains underexplored due to lack of robust functionalized MOPs. Herein we report the use of polycarboxylate cuboctahedral RhII‐MOPs for constructing highly‐connected MOFs. Cuboctahedral MOPs were functionalized with carboxylic acid groups on their 12 vertices or 24 edges through coordinative or covalent post‐synthetic routes, respectively. We then used each isolated polycarboxylate RhII‐MOP as 12‐c cuboctahedral or 24‐c rhombicuboctahedral SBBs that, upon linkage with metallic secondary building units (SBUs), afford bimetallic highly‐connected MOFs. The assembly of a pre‐synthesized 12‐c SBB with a 4‐c paddle‐wheel SBU, and a 24‐c SBB with a 3‐c triangular CuII SBU gave rise to bimetallic MOFs having ftw (4,12)‐c or rht (3,24)‐c topologies, respectively. [ABSTRACT FROM AUTHOR]

This article discusses various research articles published in the journal Angewandte Chemie International Edition. One research article by Jorge Albalad, Inhar Imaz, Daniel Maspoch, et al. explores the use of bond scission as a synthetic tool to design new molecules and materials. They demonstrate this concept by obtaining unprecedented Rh(II)-based architectures through the disassembly of metal-organic polyhedra. Another research article by Weijie Yang, Hai-Long Jiang, et al. focuses on incorporating Pd nanoparticles into MOFs for high selectivity in CO esterification. Yoshinari Sawama, et al. report on sulfonium salt reagents for introducing deuterated alkyl groups in drug discovery, while Alexis Bordet, Walter Leitner, et al. discuss the adaptivity of a catalyst in the hydrogenation of heteroaromatics. Lastly, Leticia González, et al. investigate the photophysics of [Ru(bpy)3]2+ and propose a kinetic model for its behavior. [Extracted from the article]

This document, published in the journal Angewandte Chemie, discusses various research articles in the field of chemistry. One article explores the use of bond scission as a synthetic tool to design new molecules and materials, showcasing the synthesis of Rh(II)-based architectures through the disassembly of metal-organic polyhedra. Another article focuses on the incorporation of Pd nanoparticles into MOFs for high selectivity in CO esterification. Additionally, there is a report on the use of sulfonium salt reagents for introducing deuterated alkyl groups in drug discovery, and a study on adaptive catalysts that can switch selectivity in hydrogenation reactions. Lastly, the document mentions a research article on the photophysics of [Ru(bpy)3]2+, highlighting the importance of rate-determining states in understanding its behavior. [Extracted from the article]

Supramolecular isomerism of metal–organic frameworks (MOFs) is known for several MOF structures, having direct implications on the properties of these materials. Although the synthesis of MOF isomers is mainly serendipitous in nature, achieving controlled formation of a target framework is highly relevant for practical applications. This work discusses the influence of additives and synthesis conditions on the formation of porous isomers containing Zn2+ as nodes and 2,5-dihydroxy-1,4-benzenedicarboxylate (dobdc4–) as a linker. Using solvent mixtures containing strongly coordinated molecules, e.g. N,N′-dimethylformamide (DMF) and N-methylpyrrolidone (NMP), facilitates the formation of porous structures of type [Zn2(dobdc)(S)x]·yS (S = DMF, NMP) which are built from dinuclear Zn2(O)2(CO2)3 secondary building units (SBUs) consisting of two different edge-sharing polyhedra with the Zn2+ ions in a unsaturated coordinative environment. In the presence of water, the Zn2+ dimers are converted to one-dimensional infinite Zn2+ chains, in which the number of Zn2+-linker bonds increases, therefore giving a hydrolytically more stable coordination environment. The full characterization of the isomers as well as their conversion to the most stable isomer is presented. [ABSTRACT FROM AUTHOR]