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Issue 2, 2017
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Tuning the iron redox state inside a microporous porphyrinic metal organic framework

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Abstract

Two new 3D porphyrin-based metal organic frameworks were obtained by solvothermally reacting iron(III) chloride, a free base (5,10,15,20-tetrakis[4-(2,3,4,5-tetrazolyl)phenyl]porphyrin) (H2TTPP) and either pyrazine or 1,4-diazabicyclo[2.2.2]octane (DABCO). Both MOFs displayed a 3-D open framework of the fry topology, where the inorganic building unit is a chain of corner-sharing FeN4O2 octahedra and the porphyrinic linker is metallated with iron during the reaction course, with the N-donor base bridging the iron of the porphyrinic cores. Through thorough structural and spectroscopic analyses of the pyrazine containing material the chemical formula [FeIIpzTTP(FeII1−xDMF1−xFeIIIxOHx)]n was inferred (x ≥ 0.25). Whereas the already reported carboxylate analogue is built up from a pure iron(III) inorganic chain, here spectroscopic and structural studies evidenced a mixed valence iron(II/III) state, evidencing that, in agreement with the HSAB theory, the substitution of a carboxylate function by a tetrazolate one allows redox tuning. Finally, both materials feature one-dimensional channels of ca. 8 × 12 Å within the structures with permanent microporosity.

Graphical abstract: Tuning the iron redox state inside a microporous porphyrinic metal organic framework

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Article information


Submitted
03 Nov 2016
Accepted
07 Dec 2016
First published
07 Dec 2016

Dalton Trans., 2017,46, 517-523
Article type
Paper

Tuning the iron redox state inside a microporous porphyrinic metal organic framework

B. Abeykoon, J. Grenèche, E. Jeanneau, D. Chernyshov, C. Goutaudier, A. Demessence, T. Devic and A. Fateeva, Dalton Trans., 2017, 46, 517
DOI: 10.1039/C6DT04208B

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