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Size‐Dependent Self‐Assembly of Lanthanide‐Based Coordination Frameworks with Phenanthroline‐2,9‐dicarboxylic Acid as a Preorganized Ligand in Hybrid Materials
Author(s) -
Alipour Mahboubeh,
Akintola Oluseun,
Buchholz Axel,
Mirzaei Masoud,
EshtiaghHosseini Hossein,
Görls Helmar,
Plass Winfried
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600936
Subject(s) - chemistry , lanthanide , thermogravimetric analysis , phenanthroline , cationic polymerization , crystallography , ligand (biochemistry) , counterion , ion , inorganic chemistry , polymer chemistry , organic chemistry , biochemistry , receptor
A family of lanthanide‐based inorganic–organic hybrids, [Ce 4 (PDA) 4 (H 2 O) 9 (SiW 12 O 40 )] · 6H 2 O ( 1 , PDA = 1,10‐phenanthroline‐2,9‐dicarboxylic acid), [Nd 5 (PDA) 5 (H 2 O) 13 (OH)(SiW 12 O 40 )] · 8H 2 O ( 2 ), [Sm 3 (PDA) 2 (H 2 O) 13 (OH)(SiW 12 O 40 )] · 16.5H 2 O ( 3 ), and [Dy 4 (PDA) 4 (H 2 O) 11 (SiW 12 O 40 )] · 7H 2 O ( 4 ), has been hydrothermally synthesized with the [SiW 12 O 40 ] 4– Keggin‐type anion as a building block. Characterization by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), and single‐crystal X‐ray diffraction revealed that 1 – 4 are all coordination polymers with different structural features owing to the lanthanide‐contraction effect. Compound 1 is composed of cationic layers interconnected by Keggin anions in three dimensions. Compounds 2 and 3 are 1D rectangular tubelike and 1D ladderlike coordination polymers, respectively. The Keggin anion appears to play a different role in each of these hybrid structures, as its coordination mode varies between mono‐, bi‐, and tetradentate in 3 , 1 , and 2 , respectively. In 4 , the Keggin anions only reside in the interspace between two adjacent 2D cationic layers as discrete counterions. Magnetic measurements indicate that 4 exhibits frequency‐dependent alternating‐current (ac) magnetic susceptibilities indicative of slow relaxation of the magnetization.