Issue 12, 2010
From the journal:

Chemical Society Reviews

X-ray absorption spectroscopies: useful tools to understand metallorganic frameworks structure and reactivity†

Silvia Bordiga,a   Francesca Bonino,a   Karl Petter Lillerudb  and  Carlo Lamberti*c  

* Corresponding authors

a Department of Inorganic, Physical and Materials Chemistry, NIS Centre of Excellence, and INSTM reference center, University of Turin, Via Quarello 11, 10135 Torino, Italy
E-mail: carlo.lamberti@unito.it
Fax: +39011-6707855
Tel: 39011-6707841

b inGAP centre of Research-based Innovation, Department of Chemistry, University of Oslo, Sem Saerlandsvei 26, N-0315 Oslo, Norway

c Department of Inorganic, Physical and Materials Chemistry, NIS Centre of Excellence, and INSTM reference center, University of Turin, Via P. Giuria 7, 10125 Torino, Italy

Abstract

The large unit cells, the enormous flexibility and variation in structural motifs of MOFs represent a big challenge in the characterization of MOF materials, particularly in cases where single crystal diffraction data are not available. In this critical review it is shown that in cases where only powder diffraction data are available additional structural information, particularly regarding local coordination within the inorganic cluster, are often mandatory in order to solve the structure. There are also cases where the inorganic cluster does not follow the symmetry of the overall structure. In such cases diffraction techniques will just “see” an average structure, missing the local structure: a lack that may be critical for understanding the specific properties of the material. In both cases, EXAFS spectroscopy is the tool that provides complementary structural information on the inorganic cluster and the way it binds to the ligand. Selected examples will show how EXAFS will be relevant in: (i) confirming the structure obtained from diffraction refinements; (ii) highlighting that the inorganic cornerstone has a lower symmetry with respect to that of the organic framework; (iii) obtaining the local structure of the inorganic cluster in the desolvated material when desolvation causes a partial loss of long range order; (iv) obtaining the local structure of the inorganic cluster in the desolvated material after coordination of a probe (or reactant) molecule, including cluster deformation upon molecule coordination and metal–molecule binding distance; (v) evidencing the presence of impurities in the form of amorphous extra-phases (339 references).

Graphical abstract: X-ray absorption spectroscopies: useful tools to understand metallorganic frameworks structure and reactivity

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Article information

DOI
https://doi.org/10.1039/C0CS00082E
Article type
Critical Review
Submitted
17 Aug 2010
First published
29 Oct 2010

Chem. Soc. Rev., 2010,39, 4885-4927

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X-ray absorption spectroscopies: useful tools to understand metallorganic frameworks structure and reactivity

S. Bordiga, F. Bonino, K. P. Lillerud and C. Lamberti, Chem. Soc. Rev., 2010, 39, 4885 DOI: 10.1039/C0CS00082E

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