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Rare‐Earth–Transition‐Metal Organic–Inorganic Hybrids Based on Keggin‐type Polyoxometalates and Pyrazine‐2,3‐dicarboxylate
Author(s) -
Zhang Shaowei,
Zhao Junwei,
Ma Pengtao,
Niu Jingyang,
Wang Jingping
Publication year - 2012
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100918
Subject(s) - pyrazine , ligand (biochemistry) , ethylenediamine , chemistry , lanthanide , luminescence , transition metal , crystallography , metal , rare earth , polyoxometalate , stereochemistry , inorganic chemistry , ion , materials science , catalysis , organic chemistry , mineralogy , biochemistry , receptor , optoelectronics
Abstract Five rare‐earth–transition‐metal (RE–TM) heterometal organic–inorganic hybrids based on Keggin‐type silicotungstates and mixed ligands H2pzda (pzda=pyrazine‐2,3‐dicarboxylate) and en (en=ethylenediamine) (enH2)[Cu(en)2(H2O)]2{[Cu(en)2][Cu(en)2(H2O)][(α‐SiW11 O39)RE(H2O)(pzda)]}2⋅n H2O (n≈4; RE=YIII ( 1 ), DyIII ( 2 ), YbIII ( 3 ), and LuIII ( 4 )) and [Cu(en)2(H2O)]2{[Cu(en)2]2[Cu(pzda)2][(α‐H2SiW11O39)Ce(H2O)]2}⋅n H2O ( 5 ; n≈8) have been hydrothermally synthesized and structurally characterized. Compounds 1–5 all contain the dimeric mono‐RE substituted Keggin [RE(α‐SiW11O39)]210− subunits linked by H2pzda ligands. Interestingly, 1–4 exhibit discrete structures, in which the H2pzda ligand acts as a tetradentate ligand to bind the RE and Cu cations, whereas 5 displays a 1D double‐chain architecture, in which the H2pzda ligand adopts a new pentadentate mode to connect the Ce and Cu cations. To our knowledge, 1–5 represent the first monovacant Keggin‐type silicotungstates containing both RE–TM heterometals and mixed ligands. The luminescence of 2 is derived from the combination of the DyIII cations and H2pzda ligands, whereas the luminescence properties of 1 and 3–5 are attributable to the H2pzda ligands.