High Electrical Conductivity in Three-Dimensional Porphyrin-Phosphonate Metal Organic-Frameworks

Abstract

<p>Herein, we report the design and synthesis of a highly electrically conductive and microporous three-dimensional zinc-phosphonate metal-organic framework [Zn(Cu-<i>p</i>-H<sub>4</sub>TPPA)] ⋅2 (CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub><sup>+</sup> (designated as GTUB3), constructed using the 5,10,15,20‐tetrakis [<i>p</i>‐phenylphosphonic acid] porphyrin (<i>p</i>-H<sub>8</sub>TPPA) organic linker. GTUB3 has an indirect band gap of 1.64 eV and a high average electrical conductivity of<b> </b>4 S/m, making it a rare example of an electrically conductive zinc metal-organic framework. The N<sub>2</sub>-accessible geometric surface area of GTUB3, as predicted by molecular simulations, is 671 m<sup>2</sup>/g. Owing to its simple, high-yield synthesis at low temperatures, porosity, and electrical conductivity, GTUB3 may be used as a low-cost electrode material in next generation phosphonate-supercapacitors. </p>

Tuning Structural and Optical Properties of Porphyrin‐based Hydrogen‐Bonded Organic Frameworks by Metal Insertion

“…[ 31 ] Due to the larger ionic radius of Pd, it produced the metal‐free p ‐H 8 ‐TPPA linker after its synthesis, while the Ni‐catalyzed synthesis of p ‐H 8 ‐TPPA regularly produced Ni( p ‐H 8 ‐TPPA). [ 32–35 ] The standard approach for inserting metal ions into porphyrin cores involves refluxing in a high boiling point solvent such as pyridine or DMF for hours to days. For p ‐H 8 ‐TPPA, this approach is not suitable because it may lead to phosphonate metal binding.…”