Electronic Challenges of Retrofitting 2D Electrically Conductive MOFs to Form 3D Conductive Lattices

Porous electrical conductors offer
opportunities for next-generation
energy storage solutions and electrocatalytic technologies. Metal–organic
frameworks are one of the highest porosity scaffolds but typically
feature low electrical conductivity due to their highly ionic metal–ligand
interface. In this paper, we use computational approaches to study
the inclusion of ligating pillars in a known electrically conductive
framework, Ni3(hexaimino­benzene)2. We
hypothesize that because Ni3(hexaimino­benzene)2 is an in-plane conductor, retrofitting this material may
yield a 3D-connected network with metallicity in all crystallographic
directions. However, we find that while this strategy likely yields
unstable connectivity for the Ni2+ system, the use of either
Cr2+ or Fe2+ provides a unique avenue to form
3D-connected conductors. The study further highlights the critical
role of the metal dz2 orbitals
in creating conductive metal–organic frameworks.