3D <i>vs.</i> turbostratic: controlling metal–organic framework dimensionality <i>via N</i>-heterocyclic carbene chemistry

The design of metal-organic frameworks (MOFs) having large pore sizes and volumes often requires the use of complex organic ligands, currently synthesized using costly and time-consuming palladiumcatalyzed coupling chemistry. Thus, in the present work, a new strategy for ligand design is reported, where piperazine and dihydrophenazine units are used as substitutes for benzene rings, which are the basic building block of most MOF ligands. This chemistry, which is based on simple, nucleophilic aromatic substitution (S N Ar) reactions, is used for the transition metal catalyst-free construction of 21 new, carboxylatebased ligands with varying sizes, shapes, and denticity and 15 linear di-and tetra-nitriles. Moreover, to demonstrate the utility of the ligands as building blocks, 16 new structurally diverse MOFs having surface areas up to 3100 m 2 g À 1 were also synthesized.

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A Simple, Transition Metal Catalyst‐Free Method for the Design of Complex Organic Building Blocks Used to Construct Porous Metal–Organic Frameworks

Kochetygov

Roth

Pache

et al. 2023

Angewandte Chemie

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A Simple, Transition Metal Catalyst‐Free Method for the Design of Complex Organic Building Blocks Used to Construct Porous Metal–Organic Frameworks

et al. 2023

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A Multimetal Approach for the Reticulation of Iridium into Metal–Organic Framework Building Units

Vasile,

Borrallo-Aniceto,

Esteban-Betegón

et al. 2024

J. Am. Chem. Soc.

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Noble metal elements are ubiquitous in our everyday life, from medical applications to electronic devices and synthetic chemistry. Iridium is one of the least abundant elements, and despite its scarcity, it remains essential for efficient and active catalytic processes. Consequently, the development of heterogeneous catalysts with the presence of active iridium sites is of enormous interest as it leads to the improvement of their recyclability and reusability. Here, we demonstrate a strategy to incorporate iridium atoms into metal–organic frameworks (MOFs), as part of their secondary building units (SBUs), resulting in robust and reusable materials with heterogeneous photocatalytic activity.

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3D vs. turbostratic: controlling metal–organic framework dimensionality via N-heterocyclic carbene chemistry

Abstract: Using azolium-based ligands for the construction of metal-organic frameworks (MOFs) is a viable strategy to immobilize catalytically active N-heterocyclic carbenes (NHC) or NHC-derived species inside MOF pores. Thus, in the...

Cited by 4 publications

References 55 publications

A Simple, Transition Metal Catalyst‐Free Method for the Design of Complex Organic Building Blocks Used to Construct Porous Metal–Organic Frameworks

A Simple, Transition Metal Catalyst‐Free Method for the Design of Complex Organic Building Blocks Used to Construct Porous Metal–Organic Frameworks

A Simple, Transition Metal Catalyst‐Free Method for the Design of Complex Organic Building Blocks Used to Construct Porous Metal–Organic Frameworks

A Multimetal Approach for the Reticulation of Iridium into Metal–Organic Framework Building Units

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