TY - JOUR
T1 - High-nuclearity Ni-substituted polyoxometalates
T2 - A series of poly(polyoxotungstate)s containing 20-22 nickel centers
AU - Li, Xin Xiong
AU - Zheng, Shou Tian
AU - Zhang, Jie
AU - Fang, Wei Hui
AU - Yang, Guo Yu
AU - Clemente-Juan, Juan Modesto
PY - 2011/11/11
Y1 - 2011/11/11
N2 - Three high-nuclearity Ni-substituted polyoxotungstates (POTs)-[Ni(enMe) 2(H 2O) 2] 2[Ni(H 2O) 6] 2- [Ni(enMe) 2][Ni(H 2O) 2] 1.5[HNi 20X 4W 34- (OH) 4O 136(H 2O) 6(enMe) 8]·11 H 2O (3), [Ni(en) 2(H 2O)] 2[H 8Ni 21X 4W 34(OH) 4- O 136(en) 10(H 2O) 5]·22 H 2O (4), and [Ni-(enMe) 2] 2[H 6Ni 22X 4W 34(OH) 4O 136(H 2O) 6(enMe) 10]·18 H 2O (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 6Ni 20P 4W 34(OH) 4O 136(enMe) 8- (H 2O) 6]·12 H 2O (1) and [Ni(en) 2- (H 2O)] 2[H 8Ni 20P 4W 34(OH) 4O 136(en) 9- (H 2O) 4]·16 H 2O (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 20X 4- W 34(OH) 4O 136(H 2O) 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 8Ni 21X 4W 34(OH) 4O 136(en) 10(H 2O) 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. Degradation of multilacunary precursors and the structure-directing effect of trilacunary Keggin {B-α-PW 9O 34} fragments under hydrothermal conditions in the presence of nickel ions result in formation of the largest Ni-substituted poly(polyoxotungstate)s known to date, which contain 20-22 Ni centers. The picture shows the X-ray structure of Ni 22-substituted polyanion [H 6Ni 22X 4W 34(OH) 4O 136(H 2O) 6-(enMe) 10] 4- (enMe=1,2-diaminopropane).
AB - Three high-nuclearity Ni-substituted polyoxotungstates (POTs)-[Ni(enMe) 2(H 2O) 2] 2[Ni(H 2O) 6] 2- [Ni(enMe) 2][Ni(H 2O) 2] 1.5[HNi 20X 4W 34- (OH) 4O 136(H 2O) 6(enMe) 8]·11 H 2O (3), [Ni(en) 2(H 2O)] 2[H 8Ni 21X 4W 34(OH) 4- O 136(en) 10(H 2O) 5]·22 H 2O (4), and [Ni-(enMe) 2] 2[H 6Ni 22X 4W 34(OH) 4O 136(H 2O) 6(enMe) 10]·18 H 2O (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 6Ni 20P 4W 34(OH) 4O 136(enMe) 8- (H 2O) 6]·12 H 2O (1) and [Ni(en) 2- (H 2O)] 2[H 8Ni 20P 4W 34(OH) 4O 136(en) 9- (H 2O) 4]·16 H 2O (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 20X 4- W 34(OH) 4O 136(H 2O) 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 8Ni 21X 4W 34(OH) 4O 136(en) 10(H 2O) 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. Degradation of multilacunary precursors and the structure-directing effect of trilacunary Keggin {B-α-PW 9O 34} fragments under hydrothermal conditions in the presence of nickel ions result in formation of the largest Ni-substituted poly(polyoxotungstate)s known to date, which contain 20-22 Ni centers. The picture shows the X-ray structure of Ni 22-substituted polyanion [H 6Ni 22X 4W 34(OH) 4O 136(H 2O) 6-(enMe) 10] 4- (enMe=1,2-diaminopropane).
KW - hydrothermal synthesis
KW - magnetic properties
KW - nickel
KW - polyoxometalates
KW - tungsten
UR - http://www.scopus.com/inward/record.url?scp=80555144150&partnerID=8YFLogxK
U2 - 10.1002/chem.201101496
DO - 10.1002/chem.201101496
M3 - Article
C2 - 22167882
AN - SCOPUS:80555144150
SN - 0947-6539
VL - 17
SP - 13032
EP - 13043
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 46
ER -