Million-Fold Electrical Conductivity Enhancement in Fe 2 (DEBDC) versus Mn 2 (DEBDC) (E = S, O)

Sun, Lei; Hendon, Christopher H.; Minier, Mikael A.; Walsh, Aron; Dincă, Mircea

doi:10.1021/jacs.5b02897

Title: Million-Fold Electrical Conductivity Enhancement in Fe ₂ (DEBDC) versus Mn ₂ (DEBDC) (E = S, O)

Abstract

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, DOBDC4– = 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 Mn²⁺ 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 Fe²⁺ 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.

Authors:

Sun, Lei ^[1]; Hendon, Christopher H. ^[2]; Minier, Mikael A. ^[1]; Walsh, Aron ^[2]; Dincă, Mircea ^[1]

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom

Publication Date:: Wed May 06 00:00:00 EDT 2015

Research Org.:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1179607

Alternate Identifier(s):: OSTI ID: 1345981; OSTI ID: 1454937

Grant/Contract Number:: SC0006937

Resource Type:: Published Article

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 19; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Sun, Lei, Hendon, Christopher H., Minier, Mikael A., Walsh, Aron, and Dincă, Mircea. Million-Fold Electrical Conductivity Enhancement in Fe 2 (DEBDC) versus Mn 2 (DEBDC) (E = S, O).  United States: N. p., 2015. 
Web.  doi:10.1021/jacs.5b02897.

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                    Sun, Lei, Hendon, Christopher H., Minier, Mikael A., Walsh, Aron, & Dincă, Mircea. Million-Fold Electrical Conductivity Enhancement in Fe 2 (DEBDC) versus Mn 2 (DEBDC) (E = S, O).  United States.  https://doi.org/10.1021/jacs.5b02897

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                    Sun, Lei, Hendon, Christopher H., Minier, Mikael A., Walsh, Aron, and Dincă, Mircea. Wed .  
"Million-Fold Electrical Conductivity Enhancement in Fe 2 (DEBDC) versus Mn 2 (DEBDC) (E = S, O)".  United States.  https://doi.org/10.1021/jacs.5b02897.

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@article{osti_1179607,

  title        = {Million-Fold Electrical Conductivity Enhancement in Fe 2 (DEBDC) versus Mn 2 (DEBDC) (E = S, O)},

  author       = {Sun, Lei and Hendon, Christopher H. and Minier, Mikael A. and Walsh, Aron and Dincă, Mircea},

  abstractNote = {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, DOBDC4– = 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 Mn2+ 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 Fe2+ 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.},

  doi          = {10.1021/jacs.5b02897},

  journal      = {Journal of the American Chemical Society},

  number       = 19,

  volume       = 137,

  place        = {United States},

  year         = {Wed May 06 00:00:00 EDT 2015},

  month        = {Wed May 06 00:00:00 EDT 2015}

}

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Figure 1: (a) Parts of the infinite secondary building units in M₂(DEBDC)(DMF)₂·x(DMF) (M = Fe, Mn; E = S, O). The (-M-E)_∞ chains are represented in purple. (b,c) Partial structures of Fe₂(DSBDC)(DMF)₂·x(DMF) and Fe₂(DSBDC)(DMF)₂ as determined by single-crystal X-ray diffraction and DFT structure optimization, respectively. H atoms and solvent moleculesmore »

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Title: Million-Fold Electrical Conductivity Enhancement in Fe 2 (DEBDC) versus Mn 2 (DEBDC) (E = S, O)

Abstract

Citation Formats

Figures / Tables:

Title: Million-Fold Electrical Conductivity Enhancement in Fe ₂ (DEBDC) versus Mn ₂ (DEBDC) (E = S, O)