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

The reaction of anhydrous lanthanide chlorides together with 4,4′-bipyridine yields the MOFs [Formula: see text] [Ln(2)Cl(6)(bipy)(3)]·2bipy, with Ln = Pr − Yb, bipy = 4,4′-bipyridine, and [Formula: see text] [La(2)Cl(6)(bipy)(5)]·4bipy. Post-synthetic thermal treatment in combination with different...

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Autores principales: Matthes, Philipp R., Schönfeld, Fabian, Zottnick, Sven H., Müller-Buschbaum, Klaus
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6332306/
https://www.ncbi.nlm.nih.gov/pubmed/26151112
http://dx.doi.org/10.3390/molecules200712125
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author Matthes, Philipp R.
Schönfeld, Fabian
Zottnick, Sven H.
Müller-Buschbaum, Klaus
author_facet Matthes, Philipp R.
Schönfeld, Fabian
Zottnick, Sven H.
Müller-Buschbaum, Klaus
author_sort Matthes, Philipp R.
collection PubMed
description The reaction of anhydrous lanthanide chlorides together with 4,4′-bipyridine yields the MOFs [Formula: see text] [Ln(2)Cl(6)(bipy)(3)]·2bipy, with Ln = Pr − Yb, bipy = 4,4′-bipyridine, and [Formula: see text] [La(2)Cl(6)(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. [Formula: see text] [LaCl(3)(bipy)] and [Formula: see text] [Ln(3)Cl(9)(bipy)(3)], with Ln = La, Pr, Sm, and [Formula: see text] [Ho(2)Cl(6)(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 [Formula: see text] [Gd(2)Cl(6)(qtpy)(2)(bipy)(2)]·bipy. Altogether, the manuscript elaborates the influence of thermal treatment beyond the usual activation procedures reported for MOFs.
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spelling pubmed-63323062019-01-24 Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment Matthes, Philipp R. Schönfeld, Fabian Zottnick, Sven H. Müller-Buschbaum, Klaus Molecules Article The reaction of anhydrous lanthanide chlorides together with 4,4′-bipyridine yields the MOFs [Formula: see text] [Ln(2)Cl(6)(bipy)(3)]·2bipy, with Ln = Pr − Yb, bipy = 4,4′-bipyridine, and [Formula: see text] [La(2)Cl(6)(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. [Formula: see text] [LaCl(3)(bipy)] and [Formula: see text] [Ln(3)Cl(9)(bipy)(3)], with Ln = La, Pr, Sm, and [Formula: see text] [Ho(2)Cl(6)(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 [Formula: see text] [Gd(2)Cl(6)(qtpy)(2)(bipy)(2)]·bipy. Altogether, the manuscript elaborates the influence of thermal treatment beyond the usual activation procedures reported for MOFs. MDPI 2015-07-03 /pmc/articles/PMC6332306/ /pubmed/26151112 http://dx.doi.org/10.3390/molecules200712125 Text en © 2015 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Matthes, Philipp R.
Schönfeld, Fabian
Zottnick, Sven H.
Müller-Buschbaum, Klaus
Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment
title Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment
title_full Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment
title_fullStr Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment
title_full_unstemmed Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment
title_short Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment
title_sort post-synthetic shaping of porosity and crystal structure of ln-bipy-mofs by thermal treatment
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6332306/
https://www.ncbi.nlm.nih.gov/pubmed/26151112
http://dx.doi.org/10.3390/molecules200712125
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