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Sun, Lei,Hendon, Christopher H.,Minier, Mikael A.,Walsh, Aron,Dincă,, Mircea American Chemical Society 2015 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.137 No.19
<P/><P>Reaction of FeCl<SUB>2</SUB> and H<SUB>4</SUB>DSBDC (2,5-disulfhydrylbenzene-1,4-dicarboxylic acid) leads to the formation of Fe<SUB>2</SUB>(D<B>S</B>BDC), an analogue of M<SUB>2</SUB>(D<B>O</B>BDC) (MOF-74, DOBDC<SUP>4–</SUP> = 2,5-dihydroxybenzene-1,4-dicarboxylate). The bulk electrical conductivity values of both Fe<SUB>2</SUB>(D<B>S</B>BDC) and Fe<SUB>2</SUB>(D<B>O</B>BDC) are ∼6 orders of magnitude higher than those of the Mn<SUP>2+</SUP> analogues, Mn<SUB>2</SUB>(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<SUP>2+</SUP> 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.</P>
Park, Sarah S.,Hendon, Christopher H.,Fielding, Alistair J.,Walsh, Aron,O’Keeffe, Michael,Dincă,, Mircea American Chemical Society 2017 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.139 No.10
<P>The structure-directing role of the inorganic secondary building unit (SBU) is key for determining the topology of metal organic frameworks (MOFs). Here we show that organic building units relying on strong Ir interactions that are energetically competitive with the formation of common inorganic SBUs can also play a role in defining the topology. We demonstrate the importance of the organic SBU in the formation of Mg2H6(H3O)(TTFTB)(3) (MIT-25), a mesoporous MOF with the new ssp topology. A delocalized electronic hole is critical in the stabilization of the TTF triad organic SBUs and exemplifies a design principle for future MOF synthesis.</P>