Article Review · Journal of the American Chemical Society · 2014

Ni3(HITP)2: The MOF That Conducts

PaperHigh electrical conductivity in Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2, a semiconducting metal-organic graphene analogue
AuthorsD. Sheberla, L. Sun, M. A. Blood-Forsythe, S. Er, C. R. Wade, C. K. Brozek, A. Aspuru-Guzik, M. Dinca
PublishedJournal of the American Chemical Society, 2014
DOI10.1021/ja502765n
Read the Original Paper ↗

Every MOF property surveyed so far, porosity, stability, selectivity, tolerates the materials being electrical insulators, which they overwhelmingly are: carboxylate linkages are poor electron highways. Sheberla, Dinca and colleagues broke the pattern by swapping oxygen donors for nitrogen, condensing hexaaminotriphenylene with nickel into stacked two-dimensional honeycomb sheets, a deliberate structural rhyme with graphene.

The conductivity numbers rewrote expectations: about 2 S/cm through pressed pellets and 40 S/cm across thin films, records for MOFs at the time and respectable against many conducting polymers. Extended pi-d conjugation across the nickel-diimine planes, plus graphite-like interlayer stacking, provides genuine band transport rather than the hopping conduction of doped insulators. A crystalline, porous, synthetically tunable conductor is a strange and useful object.

Critical notes: pellet measurements convolve grain boundaries with intrinsic transport, so the true single-crystal conductivity remained uncertain here, and the material sacrifices the large pores and diverse chemistry that make classical MOFs attractive, its channels are narrow and its linker options constrained. Air stability of the reduced states also required later care.

The descendants justify the hype: Ni3(HITP)2 and its relatives have since appeared in chemiresistive sensors, supercapacitor electrodes and electrocatalysts, applications structurally impossible for insulating frameworks. When a single paper creates a property axis where none existed, it belongs on any list of the field's essentials.

Reviewer's VerdictThe paper that gave MOFs a bandgap conversation. Electronics-minded chemists start here.

This review reflects the independent opinion of Team LR at MOFsResearch.com. It is an educational commentary on the cited publication and is not affiliated with or endorsed by the original authors or publisher. Verify all figures against the original paper before use.