TY - JOUR
T1 - Hydrothermal combination of trilacunary dawson phosphotungstates and hexanickel clusters
T2 - From an isolated cluster to a 3D framework
AU - Li, Xin Xiong
AU - Fang, Wei Hui
AU - Zhao, Jun Wei
AU - Yang, Guo Yu
N1 - Publisher Copyright:
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2014/12/22
Y1 - 2014/12/22
N2 - Three novel hexa-Ni-substituted Dawson phos-phortungstates [Ni6(en)3(H2O)6(μ3-OH)3(H3P2W15O56)]·14H2O (1), [Ni(enMe)2(H2O)][Ni6(enMe)3(μ3-OH)3(H2O)6(HP2W15O56)]· 10H2O (2), and [Ni(enMe)2]3[Ni(enMe)2(H2O)][Ni(enMe)(H2O)2]-[Ni6(enMe)3(μ3-OH)3(Ac)2(H2O)(P2W15O56)]2·6H2O (3) (en = eth-ylenediamine, enMe = 1, 2-diaminopropane, Ac = CH3COO-) have been made under hydrothermal conditions and were characterized by IR spectroscopy, elemental analysis, diffuse reflectance spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The common structural features of compounds 1-3 contain the similar hexa-Ni-substituted Dawson polyoxometalate (POM) units that can be viewed as a [Ni6(μ3-OH)3]9+ cluster capping on a [P2W15O56]12- fragment. Compounds 1 and 2 are two isolated clusters, whereas compound 3 is the first 3D POM framework constructed from hexa-Ni-substituted Dawson POM units and Ni(enMe) complex bridges. The preparations of compounds 1-3 not only indicate that triangle coplanar Ni6 clusters are very stable fragments in both trivacant Keggin and trivacant Dawson POM systems, but also offer that the hydrothermal technique can act as an effective strategy for making novel Dawson-type high-nuclear transition-metal cluster substituted POMs by combination of lacunary Dawson precusors with transition-metal cations in the tunable role of organic ligands. In addition, magnetic measurements illustrate that there exist overall ferromagnetic interactions in compound 3.
AB - Three novel hexa-Ni-substituted Dawson phos-phortungstates [Ni6(en)3(H2O)6(μ3-OH)3(H3P2W15O56)]·14H2O (1), [Ni(enMe)2(H2O)][Ni6(enMe)3(μ3-OH)3(H2O)6(HP2W15O56)]· 10H2O (2), and [Ni(enMe)2]3[Ni(enMe)2(H2O)][Ni(enMe)(H2O)2]-[Ni6(enMe)3(μ3-OH)3(Ac)2(H2O)(P2W15O56)]2·6H2O (3) (en = eth-ylenediamine, enMe = 1, 2-diaminopropane, Ac = CH3COO-) have been made under hydrothermal conditions and were characterized by IR spectroscopy, elemental analysis, diffuse reflectance spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The common structural features of compounds 1-3 contain the similar hexa-Ni-substituted Dawson polyoxometalate (POM) units that can be viewed as a [Ni6(μ3-OH)3]9+ cluster capping on a [P2W15O56]12- fragment. Compounds 1 and 2 are two isolated clusters, whereas compound 3 is the first 3D POM framework constructed from hexa-Ni-substituted Dawson POM units and Ni(enMe) complex bridges. The preparations of compounds 1-3 not only indicate that triangle coplanar Ni6 clusters are very stable fragments in both trivacant Keggin and trivacant Dawson POM systems, but also offer that the hydrothermal technique can act as an effective strategy for making novel Dawson-type high-nuclear transition-metal cluster substituted POMs by combination of lacunary Dawson precusors with transition-metal cations in the tunable role of organic ligands. In addition, magnetic measurements illustrate that there exist overall ferromagnetic interactions in compound 3.
KW - Dawson
KW - Hydrothermal synthesis
KW - Nickel
KW - Polyoxometalates
KW - Tungsten
UR - https://www.scopus.com/pages/publications/84920193927
U2 - 10.1002/chem.201404384
DO - 10.1002/chem.201404384
M3 - Article
C2 - 25376740
AN - SCOPUS:84920193927
SN - 0947-6539
VL - 20
SP - 17324
EP - 17332
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 52
ER -