Journal article

Publication year: 2015

Pages: 12125-12153

Journal: Molecules

Volume number: 20

Issue number: 7

ISSN: 1420-3049

DOI Link: https://doi.org/10.3390/molecules200712125

Publisher: MDPI

Abstract: 
The reaction of anhydrous lanthanide chlorides together with 4,4'-bipyridine yields the MOFs (2)(infinity)[Ln(2)Cl(6)(bipy)(3)]center dot 2bipy, with Ln = Pr-Yb, bipy = 4,4'-bipyridine, and (2)(infinity)[La2Cl6(bipy)(5)]center dot 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. (2)(infinity)[LaCl3(bipy)] and (2)(infinity)[Ln(3)Cl(9)(bipy)(3)], with Ln = La, Pr, Sm, and (1)(infinity)[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)(infinity)[Gd2Cl6(qtpy)(2)(bipy)(2)]center dot bipy. Altogether, the manuscript elaborates the influence of thermal treatment beyond the usual activation procedures reported for MOFs.

Harvard Citation style: Matthes, P., Schönfeld, F., Zottnick, S. and Müller-Buschbaum, K. (2015) Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment, Molecules, 20(7), pp. 12125-12153. https://doi.org/10.3390/molecules200712125

APA Citation style: Matthes, P., Schönfeld, F., Zottnick, S., & Müller-Buschbaum, K. (2015). Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment. Molecules. 20(7), 12125-12153. https://doi.org/10.3390/molecules200712125