Towards a potential 4,4′-(1,2,4,5-tetrazine-3,6-diyl) dibenzoic spacer to construct metal–organic frameworks

Abstract

ARTICLE This journal isThe ligand, 4,4'-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid has been designed and explored with the aim of using it as linker to construct three-dimensional metal-organic frameworks (MOFs). We have been successful in the formation of a potassium 3D-MOF with this novel linker. This compound is a three-dimensional structure where the layers formed by potassium ions and carboxylate groups are separated by this organic ligand. Luminescence and cytotoxicity studies have been performed. We have used molecular simulations to predict the porous properties of an isoreticular, analogue to IRMOF-16 based on this linker due to the similarity of the new designed ligand with p-terphenyl-4,4''-dicarboxylate present in IRMOF-16.

Tetrazine‐Based Metal‐Organic Frameworks as Scaffolds for Post‐Synthetic Modification by the Click Reaction

“…Alternatively, the modification can be done through chemical modification of the linker by “click chemistry” to introduce large reactive species into MOFs . In this respect [4+2] cycloaddition of 1,2,4,5‐tetrazines and various dienophiles, referred as inverse electron demand Diels‐Alder (IEDDA) reaction, represent an attractive reaction that allows reaction of tetrazines with wide range of unsaturated compounds . Surprisingly, only few tetrazine based MOFs have been described in the literature: Calahorro and co‐workers developed tetrazine functionalized potassium 3D MOF for luminescence and cytotoxicity studies, alternatively Nickerl et al synthetized dihydro‐1,2,4,5‐tetrazine‐3,6‐dicarboxylate Zr‐MOF by ligand exchange reaction to create an optical sensor for the detection of oxidative agents such as nitrous gases.…”

A Flexible Fluorescent Zr Carboxylate Metal–Organic Framework for the Detection of Electron-Rich Molecules in Solution

“…Indeed, Zr­(IV) carboxylate-based MOFs efficient for optical detection (mostly by fluorescence), − ,− especially of the pH, , have been reported. Regarding the fluorophore, we focused our attention on a small electron-poor luminophore, the s -tetrazine, whose fluorescence is known to be quenched by electron-rich molecules, , and which has shown useful properties and applications. − Few MOFs built up from s -tetrazine derived ligands have been reported to date, mostly based on M­(II) cations. − One of these solids was found to exhibit solvatochromism upon adsorption of solvents . Recently, Kaskel et al reported the doping of the Zr­(IV) terephthalate UiO-66 by the hydrotetrazinedicarboxylate (i.e., reduced form of s -tetrazine) for the detection of oxidative gases (nitrous gas and bromine) by redox reactions .…”

Selective CO2 Sorption Using Compartmentalized Coordination Polymers with Discrete Voids**

“…It should be emphasized that temperature is one of the most critical aspects in common separations, as an increase in energy consumption will affect the viability of industrial efficiency. This fact is particularly relevant considering that apart from CCP‐6 only a few materials are regenerated at room temperature, [28, 29] whereas most of the best performing PCPs/MOFs for these separations require regeneration temperatures of 100–200 °C, especially when CH 4 is part of the target mixture [3–34] …”