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Open AccessArticle

Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment

Institute of Inorganic Chemistry, University of Würzburg, Am Hubland, 97074 Würzburg, Germany
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Academic Editor: Dong-Sheng Li
Molecules 2015, 20(7), 12125-12153; https://doi.org/10.3390/molecules200712125
Received: 17 April 2015 / Accepted: 23 June 2015 / Published: 3 July 2015
(This article belongs to the Special Issue Metal-Organic Frameworks: Chemistry and Applications)
The reaction of anhydrous lanthanide chlorides together with 4,4′-bipyridine yields the MOFs 2[Ln2Cl6(bipy)3]·2bipy, with Ln = Pr − Yb, bipy = 4,4′-bipyridine, and 3[La2Cl6(bipy)5]·4bipy. Post-synthetic thermal treatment in combination with different vacuum conditions was successfully used to shape the porosity of the MOFs. In addition to the MOFs microporosity, a tuneable mesoporosity can be implemented depending on the treatment conditions as a surface morphological modification. Furthermore, thermal treatment without vacuum results in several identifiable crystalline high-temperature phases. Instead of collapse of the frameworks upon heating, further aggregation under release of bipy is observed. 3[LaCl3(bipy)] and 2[Ln3Cl9(bipy)3], with Ln = La, Pr, Sm, and 1[Ho2Cl6(bipy)2] were identified and characterized, which can also exhibit luminescence. Besides being released upon heating, the linker 4,4′-bipyridine can undergo activation of C-C bonding in ortho-position leading to the in-situ formation of 4,4′:2′,2′′:4′′,4′′′-quaterpyridine (qtpy). qtpy can thereby function as linker itself, as shown for the formation of the network 2[Gd2Cl6(qtpy)2(bipy)2]·bipy. Altogether, the manuscript elaborates the influence of thermal treatment beyond the usual activation procedures reported for MOFs. View Full-Text
Keywords: metal-organic frameworks; shaping of porosity; thermal treatment; Ln-MOFs; luminescence; crystal structure metal-organic frameworks; shaping of porosity; thermal treatment; Ln-MOFs; luminescence; crystal structure
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Matthes, P.R.; Schönfeld, F.; Zottnick, S.H.; Müller-Buschbaum, K. Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment. Molecules 2015, 20, 12125-12153.

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