Synthesis of a Copper 1,3,5-Triamino-2,4,6-benzenetriol Metal–Organic Framework

Abstract

We report the synthesis and characterization of a two-dimensional (2D) MX2Y2-type (M = metal, X, Y = N, S, O, and X ≠ Y) copper 1,3,5-triamino-2,4,6-benzenetriol metal–organic framework (Cu3(TABTO)2-MOF). The role of oxygen in the synthesis of this MOF was investigated. Copper metal is formed along with the MOF when the synthesis is done in argon as suggested by XRD. When the reaction was exposed to air with vigorous stirring, copper metal was not observed by XRD. However, if there is no stirring, then copper metal is formed, and we learned that this is because oxygen was not allowed to enter the solvent due to the formation of a MOF film at the air/water interface. For the sample synthesized in argon (Cu3(TABTO)2-Ar), an insulating Cu3(TABTO)2-Ar pellet (σ < 10–10 S cm–1) became a metallic conductor with an electrical conductivity of 0.78 S cm–1 at 300 K after exposure to iodine vapor. This work provides further insights into the role of oxygen in the synthesis of redox-active ligand-based MOFs, expands the family of 2D redox-active ligand-based electrically conductive MOFs, and offers more opportunities in sensing, photocatalytic, electronic, and energy-related applications.

The Synthesis of Hexaazatrinaphthylene‐Based 2D Conjugated Copper Metal‐Organic Framework for Highly Selective and Stable Electroreduction of CO2 to Methane

“…Ligands incorporated two types of coordinate sites are rare, especially with heteroatoms exposed to the pores. Except phthalocyanine, two ligands including tetraazanaphthotetraphene [9] and 1,3,5triamino-2,4,6-benzenetriol [10] with exposed nitrogen sites have been recently reported. The incorporated and exposed heteroatoms would open up new opportunities to explore novel applications, nevertheless the synthesis of this class of 2D MOF has a great challenge due to the competition coordination between different sites.…”

A chalcogenide-cluster-based semiconducting nanotube array with oriented photoconductive behavior

“…23 ), show a significantly steep dispersion with an energy difference of ~ 0.71 eV (0.63 eV) along with the Γ → A (K → H and M → L) directions in reciprocal space, corresponding to the tubular direction (or c axis) in real space, while for other paths with high symmetry points, the dispersion widths are small (maximum energy difference < 0.1 eV). The relatively large dispersion strength of the energy bands indicates the facile transport of charge carriers along the c direction 42 , 49 , which is of paramount importance to photoconductive devices. Moreover, the narrow bandwidth and flat band lines near the VBM were attributed to the relatively larger localization of the Cu d orbital compared with the Ge s orbital.…”

An Unprecedented Chalcogenide-cluster-based Semiconducting Nanotube Array with Oriented Photoconductive Behavior

“…23), show a signi cantly steep dispersion with an energy difference of ~ 0.71 eV (0.63 eV) along the Γ→A (K→H and M→L) directions in reciprocal space, corresponding to the tubular direction (or c axis) in real space, while for other paths with high symmetry points, the dispersion widths are small (maximum energy difference < 0.1 eV). The relatively large dispersion strength of the energy bands indicates the facile transport of charge carriers along the c direction, 38,44 which is of paramount importance to photoconductive devices. Moreover, the narrow band width and at band lines near the VBM were attributed to the relatively larger localization of the Cu d orbital compared to the Ge s orbital.…”