Million-Fold Electrical Conductivity Enhancement in Fe2(DEBDC) versus Mn2(DEBDC) (E = S, O).
Reaction of FeCl2 and H4DSBDC (2,5-disulfhydrylbenzene-1,4-dicarboxylic acid) leads to the formation of Fe2(DSBDC), an analogue of M2(DOBDC) (MOF-74, DOBDC(4-) = 2,5-dihydroxybenzene-1,4-dicarboxylate). The bulk electrical conductivity values of both Fe2(DSBDC) and Fe2(DOBDC) are ∼6 orders of magnitude higher than those of the Mn(2+) analogues, Mn2(DEBDC) (E = O, S). Because the metals are of the same formal oxidation state, the increase in conductivity is attributed to the loosely bound Fe(2+) β-spin electron. These results provide important insight for the rational design of conductive metal-organic frameworks, highlighting in particular the advantages of iron for synthesizing such materials.
†Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Lei
L
Sun
‡Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom.
Christopher H
CH
Hendon
†Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Mikael A
MA
Minier
‡Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom.
Aron
A
Walsh
†Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Mircea
M
Dincă