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High‐Nuclearity Ni‐Substituted Polyoxometalates: A Series of Poly(polyoxotungstate)s Containing 20–22 Nickel Centers
Author(s) -
Li XinXiong,
Zheng ShouTian,
Zhang Jie,
Fang WeiHui,
Yang GuoYu,
ClementeJuan Juan Modesto
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201101496
Subject(s) - nickel , polyoxometalate , chemistry , series (stratigraphy) , polymer chemistry , crystallography , inorganic chemistry , organic chemistry , catalysis , geology , paleontology
Three high‐nuclearity Ni‐substituted polyoxotungstates (POTs)—[Ni(enMe) 2 (H 2 O) 2 ] 2 [Ni(H 2 O) 6 ] 2 ‐ [Ni(enMe) 2 ][Ni(H 2 O) 2 ] 1.5 [HNi 20 X 4 W 34 ‐ (OH) 4 O 136 (H 2 O) 6 (enMe) 8 ] ⋅ 11 H 2 O ( 3 ), [Ni(en) 2 (H 2 O)] 2 [H 8 Ni 21 X 4 W 34 (OH) 4 ‐ O 136 (en) 10 (H 2 O) 5 ] ⋅ 22 H 2 O ( 4 ), and [Ni‐(enMe) 2 ] 2 [H 6 Ni 22 X 4 W 34 (OH) 4 O 136 (H 2 O) 6 (enMe) 10 ] ⋅ 18 H 2 O ( 5 ), in which en=ethylenediamine, enMe=1,2‐diaminopropane, X=0.5 P+0.5 Ge—were made under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The structures of 3 – 5 can be viewed as novel derivatives of [H 6 Ni 20 P 4 W 34 (OH) 4 O 136 (enMe) 8 ‐ (H 2 O) 6 ] ⋅ 12 H 2 O ( 1 ) and [Ni(en) 2 ‐ (H 2 O)] 2 [H 8 Ni 20 P 4 W 34 (OH) 4 O 136 (en) 9 ‐ (H 2 O) 4 ] ⋅ 16 H 2 O ( 2 ), which both contain 20 nickel ions per structural unit. Compound 3 is the first example of a 1D cluster chain constructed from Ni 20 ‐substituted polyanions [HNi 20 X 4 ‐ W 34 (OH) 4 O 136 (H 2 O) 6 (enMe) 8 ] 11− and [Ni(enMe) 2 ] 2+ bridges. Compound 4 is a novel cluster–organic chain built by Ni 21 ‐substituted polyanions [H 8 Ni 21 X 4 W 34 (OH) 4 O 136 (en) 10 (H 2 O) 5 ] 4− and en molecule bridges. Compound 5 is a discrete POT with 22 Ni centers, and is not only the largest nickel‐substituted POT, but also contains the highest number of nickel ions in one polyanion to date. Magnetic measurements illustrate that overall ferromagnetic interactions exist in 1 – 5 . The magnetic behavior of 1 and 2 was theoretically simulated by the MAGPACK magnetic program package.