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Surface‐grafted lanthanoid complexes of the tungstosilicate polyanion [SiW 12 O 40 ] 4− : a synthetic, structural and computational investigation
Author(s) -
Derakhshanrad Shadi,
Mirzaei Masoud,
Najafi Atefeh,
Ritchie Chris,
Bauzá Antonio,
Frontera Antonio,
Mague Joel T.
Publication year - 2018
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229618009580
Subject(s) - crystallography , chemistry , supramolecular chemistry , lanthanide , praseodymium , hydrogen bond , infrared spectroscopy , intermolecular force , hydrothermal synthesis , crystal structure , molecule , stereochemistry , hydrothermal circulation , ion , inorganic chemistry , organic chemistry , seismology , geology
As an extension of our continued interest in the preparation of inorganic–organic hybrids, we report the successful hydrothermal synthesis of sodium tris[triaqua(μ‐1,10‐phenanthroline‐2,9‐dicarboxylato)dysprosium(III)] silicododecatungstate dodecahydrate, {[DyNa(C 14 H 6 N 2 O 4 ) 3 (H 2 O) 9 (SiW 12 O 40 )]·12H 2 O} n or Na[Dy(PDA)(H 2 O) 3 ] 3 [SiW 12 O 40 ]·12H 2 O ( 1 ), and sodium aqua tris[tetraaqua(μ‐4‐hydroxypyridine‐2,6‐dicarboxylato)praseodymium(III)] silicododecatungstate dodecahydrate, {[NaPr(C 7 H 3 NO 5 ) 3 (H 2 O) 13 (SiW 12 O 40 )]·12H 2 O} n or Na(H 2 O)[Pr(pydc‐OH)(H 2 O) 4 ] 3 [SiW 12 O 40 ]·12H 2 O ( 2 ) (in which H 2 PDA is 1,10‐phenanthroline‐2,9‐dicarboxylic acid and H 2 pydc‐OH is 4‐hydroxypyridine‐2,6‐dicarboxylic acid or chelidamic acid). Both compounds have been characterized using elemental analysis, IR spectroscopy and X‐ray diffraction methods. Structural characterization by single‐crystal X‐ray diffraction reveals that these compounds consist of [SiW 12 O 40 ] 4− Keggin‐type polyoxometalates (POMs), where a single {W 3 O 13 } triad is decorated with a trinuclear Ln complex. Moreover, the decorated polyanions are involved in a series of intermolecular interactions, such as hydrogen bonds and anion–π interactions, resulting in three‐dimensional supramolecular architectures. Density functional theory (DFT) studies were conducted to support these intermolecular interactions in both 1 and 2 , and have been rationalized using molecular electrostatic potential (MEP) surface calculations.