The number of synthetic strategies used to functionalize MOFs with polymers is rapidly growing; this stems from the knowledge that non-native polymeric guests can significantly boost MOF performance in a number of desirable applications. The current work presents a scalable and solid-state method for MOF/polymer composite production. This simple method constitutes mixing a MOF powder, namely, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate), with a biomass-derived solid monomer, 5-hydroxymethylfurfural (HMF), and subsequently heating the solids; the latter promotes both solid-state diffusion of HMF into the MOF and the formation of polymeric humin species with a high density of accessible hydroxyl functionality within the MOF pore. The resulting composite, Fe-BTC/humin, was found to selectively extract Ag + ions from laundry wastewater. Subsequent reduction of the Ag + species yields a novel catalyst, Fe-BTC/humin/Ag, that is able to drive the organic transformation of cinnamaldehyde in a highly selective manner. Moreover, the catalyst exhibited recyclability up to five cycles, which is in contrast to the Fe-BTC/Ag catalyst without the humin-based polymer. It is envisioned that MOF/polymer composites that are able to selectively extract precious metals from liquid waste streams can be used for the future production of sustainable catalysts; this work was aimed at demonstrating a proof of concept in this regard. Moreover, this study brings more understanding of the impact that MOFs can have on polymer functionalities. Understanding the polymer structure and how it can be manipulated will help us realize the high degree of future potential of this distinct class of composite materials.

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.

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...

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.