TY - JOUR
T1 - Trigonal Pyramidal {AsO2(OH)} Bridging Tetranuclear Rare-Earth Encapsulated Polyoxotungstate Aggregates
AU - Li, Hailou
AU - Liu, Yajie
AU - Zheng, Rui
AU - Chen, Lijuan
AU - Zhao, Jun Wei
AU - Yang, Guo Yu
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/5/2
Y1 - 2016/5/2
N2 - The one-pot assembly reaction of Na2WO4·2H2O, RE(NO3)3·6H2O, and NaAsO2 in the participation of dimethylamine hydrochloride as an organic solubilizing agent in the acidic aqueous solution led to a class of trigonal pyramidal {AsO2(OH)} bridging rare-earth substituted arsenotungstate (AT) aggregates [H2N(CH3)2]8Na8{[W3RE2(H2O)8AsO8(OH)][B-α-AsW9O33]2}2·65H2O [RE = EuIII (1), GdIII (2), TbIII (3), DyIII (4), HoIII (5), YIII (6)], which were structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and thermogravimetric (TG) analyses. The common structural feature of 1-6 is that their polyoxoanions consist of a novel tetrameric unit [(W3RE2(H2O)8AsO8(OH))(B-α-AsW9O33)2]216- constituted by four trivacant Keggin [α-AsW9O33]9- fragments linked through an unseen elliptical [W6RE4(H2O)16As2O16(OH)2]20+ moiety. Their polyoxoanionic infrastructures can also be described as a fusion of two equivalent dimeric subunits [(W3RE2(H2O)8O7)(B-α-AsW9O33)2]8- bridged via two μ2-{AsO2(OH)} linkers. To the best of our knowledge, such a linking mode with trigonal pyramidal {AsO2(OH)} groups as linkers connecting adjacent RE containing polyoxometalate moieties together is very rare. The thermal stability of 1-6 was also investigated on the crystalline samples, and the thermal decomposition processes of 1, 4, and 6 were comparatively deeply studied. The fluorescent properties and decay times of 1, 3, and 4 were measured, and they exhibit the characteristic emissions of RE centers. The lifetimes of 1 and 3 mainly originate from the contribution of RE ions whereas the overall lifetime of 4 is contributed by the synergistic interactions of AT fragments and Dy3+ ions.
AB - The one-pot assembly reaction of Na2WO4·2H2O, RE(NO3)3·6H2O, and NaAsO2 in the participation of dimethylamine hydrochloride as an organic solubilizing agent in the acidic aqueous solution led to a class of trigonal pyramidal {AsO2(OH)} bridging rare-earth substituted arsenotungstate (AT) aggregates [H2N(CH3)2]8Na8{[W3RE2(H2O)8AsO8(OH)][B-α-AsW9O33]2}2·65H2O [RE = EuIII (1), GdIII (2), TbIII (3), DyIII (4), HoIII (5), YIII (6)], which were structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and thermogravimetric (TG) analyses. The common structural feature of 1-6 is that their polyoxoanions consist of a novel tetrameric unit [(W3RE2(H2O)8AsO8(OH))(B-α-AsW9O33)2]216- constituted by four trivacant Keggin [α-AsW9O33]9- fragments linked through an unseen elliptical [W6RE4(H2O)16As2O16(OH)2]20+ moiety. Their polyoxoanionic infrastructures can also be described as a fusion of two equivalent dimeric subunits [(W3RE2(H2O)8O7)(B-α-AsW9O33)2]8- bridged via two μ2-{AsO2(OH)} linkers. To the best of our knowledge, such a linking mode with trigonal pyramidal {AsO2(OH)} groups as linkers connecting adjacent RE containing polyoxometalate moieties together is very rare. The thermal stability of 1-6 was also investigated on the crystalline samples, and the thermal decomposition processes of 1, 4, and 6 were comparatively deeply studied. The fluorescent properties and decay times of 1, 3, and 4 were measured, and they exhibit the characteristic emissions of RE centers. The lifetimes of 1 and 3 mainly originate from the contribution of RE ions whereas the overall lifetime of 4 is contributed by the synergistic interactions of AT fragments and Dy3+ ions.
UR - https://www.scopus.com/pages/publications/84966318655
U2 - 10.1021/acs.inorgchem.6b00061
DO - 10.1021/acs.inorgchem.6b00061
M3 - Article
AN - SCOPUS:84966318655
SN - 0020-1669
VL - 55
SP - 3881
EP - 3893
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 8
ER -