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Title: Structural and Electronic Effects on the Properties of Fe2(dobdc) upon Oxidation with N2O

Journal Article · · Inorganic Chemistry
 [1];  [2];  [1];  [3];  [3];  [1];  [4];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Humboldt Univ. of Berlin (Germany)
  3. Univ. of Minnesota, Minneapolis, MN (United States); University of California, Berkeley, CA (United States)
  4. Univ. of Minnesota, Minneapolis, MN (United States); University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations

Here, we report electronic, vibrational, and magnetic properties, together with their structural dependences, for the metal–organic framework Fe2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) and its derivatives, Fe2(O)2(dobdc) and Fe2(OH)2(dobdc)—species arising in the previously proposed mechanism for the oxidation of ethane to ethanol using N2O as an oxidant. Magnetic susceptibility measurements reported for Fe2(dobdc) in an earlier study and reported in the current study for FeII0.26[FeIII(OH)]1.74(dobdc)(DMF)0.15(THF)0.22, which is more simply referred to as Fe2(OH)2(dobdc), were used to confirm the computational results. Theory was also compared to experiment for infrared spectra and X-ray powder diffraction structures. Structural and magnetic properties were computed by using Kohn-Sham density functional theory both with periodic boundary conditions and with cluster models. In addition, we studied the effects of different treatments of the exchange interactions on the magnetic coupling parameters by comparing several approaches to the exchange-correlation functional: generalized gradient approximation (GGA), GGA with empirical Coulomb and exchange integrals for 3d electrons (the GGA+U method), nonseparable gradient approximation with empirical Coulomb and exchange integrals for 3d electrons (GAM+U), hybrid GGA, meta-GGA, and hybrid meta- GGA. We found the coupling between the metal centers to be ferromagnetic in the case of Fe2(dobdc) and antiferromagnetic in the cases of Fe2(O)2(dobdc) and Fe2(OH)2(dobdc). The shift in magnetic coupling behavior correlates with the changing electronic structure of the framework, which derives from both structural and electronic changes that occur upon metal oxidation and addition of the charge-balancing oxo and hydroxo ligands.

Research Organization:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
SC0008688; FG02-12ER16362
OSTI ID:
2311157
Alternate ID(s):
OSTI ID: 2315017
Journal Information:
Inorganic Chemistry, Vol. 55, Issue 10; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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