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|Title:||Multifunctional micro-and nanosized metalorganic frameworks assembled from bisphosphonates and lanthanides|
|Author:||Vilela, Sergio M. F.|
Fernandes, Jose A.
Gomes, Ana C.
Silva, Nuno J. O.
Rodrigues, Marcelo O.
Tome, Joao P. C.
Valente, Anabela A.
Carlos, Luis D.
Paz, Filipe A. Almeida
CAMBRIDGE STRUCTURAL DATABASE
POWDER DIFFRACTION DATA
|Publisher:||ROYAL SOC CHEMISTRY|
|Abstract:||Phase-pure and highly crystalline [Ln(Hpmd)(H2O)] materials [where Ln(3)+ Eu-3+ (1), Gd-3+ (2) and Tb-3+ (3); H(4)pmd 1,4-phenylenebis(methylene) diphosphonic acid] were prepared by using three distinct approaches: (i) conventional hydrothermal synthesis (180 degrees C, 3 days); (ii) microwave-assisted heating (50 W irradiation power, 40 degrees C, 5 seconds; nano-sized aggregates with sizes ranging between 100 and 150 nm); and (iii) ultrasound-assisted synthesis which, for highly diluted reactive mixtures (Ln(3)+ : H4pmd : H2O of 1 : 1 : 7200), permitted the preparation of isolated nano-crystals at ambient temperature with 5 minutes of ultrasonic irradiation. Compounds were structurally characterized by powder X-ray diffraction (Rietveld refinement and variable-temperature studies), thermogravimetry, vibrational spectroscopy, elemental analysis and electron microscopy (SEM andEDS). The magnetic behavior of 1 and 2 was investigated between ambient temperature and ca. 2 K revealing that the Ln(3)+ cations act as isolated centers. A strategy to calculate the vibrational spectra of MOF structures and based on the known embedded-clusters approach is proposed and applied to [ Ln(Hpmd)(H2O)]. This allowed the identification, along with deuteration of the materials, of the vibrational modes of the confined water molecule in the structure. Compound 1 was tested in the methanolysis of styrene oxide at 55 degrees C: it is shown that microcrystalline 1 (1-m) does not possess significant catalytic activity; on the other hand, the nano-sized counterpart (1-n) exhibits relatively high catalytic activity and excellent selectivity to 2-methoxy-2-phenylethanol (100% yield within 48 h of reaction time). Photoluminescence studies both at ambient and low temperatures showed, on the one hand, that bulk materials are composed of a single lanthanide site and, on the other hand, that the organic linker is a suitable sensitizerof Tb-3+ (absolute quantum yield of ca. 14% for 3). It is further demonstrated that the coordinated water molecule has a pivotal role in the quenching of the photoluminescence of Eu-3+ in 1: deuteration of the material results in a ca. 3.4 times improvement of the decay time (e. g., at 300 K the lifetime improves from 0.58 +/- 0.01 ms to 1.98 +/-0.01 ms).|
|Appears in Collections:||CICECO - Artigos|
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