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Molecules 2015, 20(7), 12125-12153; doi:10.3390/molecules200712125

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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Author to whom correspondence should be addressed.
Academic Editor: Dong-Sheng Li
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)
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Abstract

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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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

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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