TY - JOUR
T1 - Symmetry breaking of α-[H2W12O 40]6- depends on the transformation of isopolyoxotungstates
AU - Chi, Ying Nan
AU - Shen, Pan Pan
AU - Cui, Feng Yun
AU - Lin, Zheng Guo
AU - Chen, Shi Lu
AU - Hu, Chang Wen
PY - 2014/5/19
Y1 - 2014/5/19
N2 - Two enantiotopic 1D chain compounds, [Cu3(L1)3(H 2O)2(H2W12O40)] ·4H2O (1a,b; L1 = 2-(4,6-bis(pyridin-2-yl)pyridin-2-yl) pyridine), crystallizing in the chiral space group P212 121 were prepared and spontaneously resolved in the absence of any chiral source. Interestingly, compounds 1a,b can be prepared from a [W7O24]6- aqueous solution, [(n-C 4H9)4N]4[W10O 32], or Na10[H2W12O42], but when [H2W12O40]6- aqueous solution was the starting material, the achiral compound [CuL1] 2[H4W12O40]·5H2O (2) was obtained. When a terpyridine ligand (L2) having a coordination mode similar to that of L1 was used, the mesomeric dimer [Cu3(L2) 3(H2O)(H2W12O40)] 2·4H2O (3) was obtained from [W7O 24]6- aqueous solution or Na10[H 2W12O42], but from [H2W 12O40]6- aqueous solution only compound [Cu2(L2)2Cl2]2[W10O 32] (4) was isolated. It is notable that in compounds 1a,b and 3 the symmetry of the α-[H2W12O40]6- cluster is broken by asymmetric coordination with metal-organic units in a similar mode. As the asymmetric subunit based on a tridecorated [H 2W12O40]6- cluster can be obtained from several isopolyoxotungstate sources except for [H2W 12O40]6-, we speculate that the symmetry breaking of α-[H2W12O40]6- depends on the transformation of isopolyoxotungstates. Furthermore, during the transformation a possible reaction intermediate as the precursor for 1a,b, compound [Cu3(L1)3(H2O)3(H 4W11O38)] (5), has been presented and characterized by density functional theory (DFT) calculations.
AB - Two enantiotopic 1D chain compounds, [Cu3(L1)3(H 2O)2(H2W12O40)] ·4H2O (1a,b; L1 = 2-(4,6-bis(pyridin-2-yl)pyridin-2-yl) pyridine), crystallizing in the chiral space group P212 121 were prepared and spontaneously resolved in the absence of any chiral source. Interestingly, compounds 1a,b can be prepared from a [W7O24]6- aqueous solution, [(n-C 4H9)4N]4[W10O 32], or Na10[H2W12O42], but when [H2W12O40]6- aqueous solution was the starting material, the achiral compound [CuL1] 2[H4W12O40]·5H2O (2) was obtained. When a terpyridine ligand (L2) having a coordination mode similar to that of L1 was used, the mesomeric dimer [Cu3(L2) 3(H2O)(H2W12O40)] 2·4H2O (3) was obtained from [W7O 24]6- aqueous solution or Na10[H 2W12O42], but from [H2W 12O40]6- aqueous solution only compound [Cu2(L2)2Cl2]2[W10O 32] (4) was isolated. It is notable that in compounds 1a,b and 3 the symmetry of the α-[H2W12O40]6- cluster is broken by asymmetric coordination with metal-organic units in a similar mode. As the asymmetric subunit based on a tridecorated [H 2W12O40]6- cluster can be obtained from several isopolyoxotungstate sources except for [H2W 12O40]6-, we speculate that the symmetry breaking of α-[H2W12O40]6- depends on the transformation of isopolyoxotungstates. Furthermore, during the transformation a possible reaction intermediate as the precursor for 1a,b, compound [Cu3(L1)3(H2O)3(H 4W11O38)] (5), has been presented and characterized by density functional theory (DFT) calculations.
UR - http://www.scopus.com/inward/record.url?scp=84901020272&partnerID=8YFLogxK
U2 - 10.1021/ic500062j
DO - 10.1021/ic500062j
M3 - Article
C2 - 24801637
AN - SCOPUS:84901020272
SN - 0020-1669
VL - 53
SP - 5029
EP - 5036
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 10
ER -