Fe(iii)-carboxythiolate layered metal–organic frameworks with interest as active materials for rechargeable alkali-ion batteries

Abstract

Metal Organic Frameworks (MOFs) built up from metal-sulfur (M-S) bonds have shown great promises in the last decade thanks to their impressive electronic properties arising from the more covalent nature...

A redox active rod coordination polymer from tetrakis(4-carboxylic acid biphenyl)tetrathiafulvalene

“…21 While early reports described non-porous conductive coordination polymers with materials such as dicyanoquinonediimine-Cu or tetracyanoquinodimethane-Cu ( σ in the 5 to 5 × 10 7 S m −1 range), 22–24 it is only in the late 2000s that electroactive coordination polymers were devised using pyrazine dithiolates, 25,26 benzene-hexathiolate or tetrathiafulvalene-tetracarboxylic acid as redox active ligands. 27,28 Such redox active materials, if embedded with accessible pores, are expected to find applications in electrochemical sensing, 29,30 thermoelectrics, 31 fuel cells, 32 batteries, 33,34 and supercapacitors. 35–37 The redox behaviour of these materials is based on structure related charge-transport mechanisms such as through-bond, 38,39 through-space or redox hopping.…”

Eu(III) Guests Sensitized by a Metal–Organic Framework for Sensing Cr(VI) in Strong Acids

“…Since its debut in 2009, , the linker molecule H 2 DMBD (2,5-dimercaptobenzenedicarboxylic acid) has opened two directions for coordination network [also known as the metal–organic framework (MOF)] materials. On one hand, transition metal ions (e.g., M = Cu + , Fe 2+ , Co 2+ , and Ni 2+ ) and other soft metal ions (Pb 2+ ) engage the thiol groups (−SH) to form solid frameworks with enhanced conductive and electroactive properties. − Highlights here include the 2D system M 2 DMBD reported in 2022, − which was also shown to be amenable with ion intercalations between the metal–thiolate layers, so as to conveniently modify the electronic and redox properties . On the other hand, very hard metal ions (e.g., Eu 3+ , Al 3+ , and Zr 4+ ) selectively engage the carboxyl units to form open frameworks (e.g., the now commercialized ZrDMBD solid), with free-standing mercapto groups for functionalization.…”

“…3−7 Highlights here include the 2D system M 2 DMBD reported in 2022, 8−10 which was also shown to be amenable with ion intercalations between the metal−thiolate layers, so as to conveniently modify the electronic and redox properties. 11 On the other hand, very hard metal ions (e.g., Eu 3+ , Al 3+ , and Zr 4+ ) selectively engage the carboxyl units to form open frameworks 12 (e.g., the now commercialized ZrDMBD solid 13 ), with freestanding mercapto groups for functionalization. Notably, the − SH groups can take up metal ion guests to afford catalytic and electronic properties; 14−20 the − SH groups (as in ZrDMBD) can also be oxidized into the − SO 3 H groups (as in ZrDSBD; DSBD: 2,5-disulfobenzenedicarboxylate) to enhance the ionic and acidic properties (e.g., for proton conductivity) of the porous host.…”