TY - JOUR
T1 - Hydrothermal synthesis of a one-dimensional bimetallic, mixed valence oxide (see abstract)
AU - Burkholder, Eric
AU - Golub, Vladimir
AU - O'Connor, Charles J.
AU - Zubieta, Jon
N1 - Funding Information:
This work was supported by a grant from the National Science Foundation, CHE-0242153.
PY - 2004/3
Y1 - 2004/3
N2 - The hydrothermal reaction of Na2WO4·2H 2O, CuSO4·5H2O, 2,2′:6′, 2″-terpyridine (terpy), H3PO4 and H2O at 150°C for 120 h yielded a mixture of [{Cu4(terpy) 4(PO4)(H2O)2}{W12O 36(PO4)}]·5H2O (1·5H 2O) and [{Cu(terpy)(H2O)2}2{W 12O36(PO4)}]·6H2O (2·6H2O). The structure of 2 consists of discrete {W 12O36(PO4)}4- Keggin clusters whose surface is decorated by two {Cu(terpy)(H2O)}2+ charge-compensating subunits. In contrast, the structure of 1 is one-dimensional with the chain constructed from {W12O 36(PO4)}5- Keggin clusters and the cationic {Cu4(terpy)4(PO4)(H2O) 2}5+ clusters. Both materials are mixed valence. In the case of 1, the tungstate core is formally {W10(VI)W2(V)}, while for 2 the oxidation states are {W11(VI)W(V)}. Crystal data: C30H27N6Cu2W6O 24.5P (1·5H2O), monoclinic, C2/c, a=14.5025(6) Å, b=22.2102(9) Å, c=26.566(1) Å, β=101.813(1)°, V=8375.6(6) Å3, Z=8. C15H21N 3CuO25W6P0.5 (2·6H 2O), monoclinic, C2/c, a=17.6263(9) Å, b=16.6990(9) Å, a=22.944(1) Å, β=112.285(1)°, V=6249.0(6) Å3, Z=8.
AB - The hydrothermal reaction of Na2WO4·2H 2O, CuSO4·5H2O, 2,2′:6′, 2″-terpyridine (terpy), H3PO4 and H2O at 150°C for 120 h yielded a mixture of [{Cu4(terpy) 4(PO4)(H2O)2}{W12O 36(PO4)}]·5H2O (1·5H 2O) and [{Cu(terpy)(H2O)2}2{W 12O36(PO4)}]·6H2O (2·6H2O). The structure of 2 consists of discrete {W 12O36(PO4)}4- Keggin clusters whose surface is decorated by two {Cu(terpy)(H2O)}2+ charge-compensating subunits. In contrast, the structure of 1 is one-dimensional with the chain constructed from {W12O 36(PO4)}5- Keggin clusters and the cationic {Cu4(terpy)4(PO4)(H2O) 2}5+ clusters. Both materials are mixed valence. In the case of 1, the tungstate core is formally {W10(VI)W2(V)}, while for 2 the oxidation states are {W11(VI)W(V)}. Crystal data: C30H27N6Cu2W6O 24.5P (1·5H2O), monoclinic, C2/c, a=14.5025(6) Å, b=22.2102(9) Å, c=26.566(1) Å, β=101.813(1)°, V=8375.6(6) Å3, Z=8. C15H21N 3CuO25W6P0.5 (2·6H 2O), monoclinic, C2/c, a=17.6263(9) Å, b=16.6990(9) Å, a=22.944(1) Å, β=112.285(1)°, V=6249.0(6) Å3, Z=8.
KW - Building block approach to oxides
KW - Mixed valence materials
KW - Polyoxotungstate
KW - Tetranuclear copper phosphate cluster
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U2 - 10.1016/j.inoche.2003.12.008
DO - 10.1016/j.inoche.2003.12.008
M3 - Article
AN - SCOPUS:1242321139
SN - 1387-7003
VL - 7
SP - 363
EP - 366
JO - Inorganic Chemistry Communications
JF - Inorganic Chemistry Communications
IS - 3
ER -