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  • Title: Reversible breaking and forming of metal-ligand coordination bonds: temperature-triggered single-crystal to single-crystal transformation in a metal-organic framework.
    Author: Bernini MC, Gándara F, Iglesias M, Snejko N, Gutiérrez-Puebla E, Brusau EV, Narda GE, Monge MA.
    Journal: Chemistry; 2009; 15(19):4896-905. PubMed ID: 19322845.
    Abstract:
    Yb(C(4)H(4)O(4))(1.5)] undergoes a temperature-triggered single-crystal to single-crystal transformation. Thermal X-ray single-crystal studies showed a reversibly orchestrated rearrangement of the atoms generated by the breaking/formation of coordination bonds, in which the stoichiometry of the compound remains unchanged. The transformation occurs on heating the crystal at approximately 130 degrees C. This uncommon behavior was also studied by thermal methods, FTIR spectroscopy, and thermodiffractometry. Both polymorphs, alpha (room-temperature form) and beta (high-temperature form), are proven to be active heterogeneous catalysts; the higher catalytic activity of beta is owed to a decrease in the Yb coordination number. A mechanism based on spectroscopic evidence and involving formation of the active species Yb-O-OH is proposed for the sulfide oxidation.
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