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Pressure‐Induced Bond Rearrangement and Reversible Phase Transformation in a Metal–Organic Framework
Author(s) -
Spencer Elinor C.,
Kiran Mangalampalli S. R. N.,
Li Wei,
Ramamurty Upadrasta,
Ross Nancy L.,
Cheetham Anthony K.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201310276
Subject(s) - crystallography , chemistry , cope rearrangement , phase (matter) , transition metal , phase transition , metal , chemical physics , materials science , stereochemistry , thermodynamics , organic chemistry , physics , catalysis
Pressure‐induced phase transformations (PIPTs) occur in a wide range of materials. In general, the bonding characteristics, before and after the PIPT, remain invariant in most materials, and the bond rearrangement is usually irreversible due to the strain induced under pressure. A reversible PIPT associated with a substantial bond rearrangement has been found in a metal–organic framework material, namely [tmenH 2 ][Er(HCOO) 4 ] 2 (tmenH 2 2+ = N , N , N ′, N ′‐tetramethylethylenediammonium). The transition is first‐order and is accompanied by a unit cell volume change of about 10 %. High‐pressure single‐crystal X‐ray diffraction studies reveal the complex bond rearrangement through the transition. The reversible nature of the transition is confirmed by means of independent nanoindentation measurements on single crystals.