Lanthanide Complexes of [-2-P2W17O61]10-: Solid State and Solution Studies
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- 作者：Qunhui Luo ; Robertha C. Howell ; Judit Bartis ; Michaela Dankova ; William DeW. Horrocks ; Jr. ; Arnold L. Rheingold ; and Lynn C. Francesconi
- 刊名：Inorganic Chemistry
- 出版年：2002
- 出版时间：November 18, 2002
- 年：2002
- 卷：41
- 期：23
- 页码：6112 - 6117
- 全文大小：108K
- 年卷期：v.41,no.23(November 18, 2002)
- ISSN：1520-510X
文摘
We have isolated the 1:1 Ln:[![]()
C="/images/gifchars/alpha.gif" BORDER=0>-2-P2W17O61]10- complexes for a series of lanthanides. The single-crystal X-raystructure of the Eu3+ analogue reveals two identical [Eu(H2O)3(
chars/alpha.gif" BORDER=0>-2-P2W17O61)]7- moieties connected through twoEu-O-W bonds, one from each polyoxometalate unit. An inversion center relates the two polyoxometalate units.The Eu(III) ion is substituted for a [WO]4+ unit in the "cap" region of the tungsten-oxygen framework of the parentWells-Dawson ion. The point group of the dimeric molecule is Ci. The extended structure is composed of the[Eu(H2O)3(chars/alpha.gif" BORDER=0>-2-P2W17O61)]214- anions linked together by surface-bound potassium cations. The space group is P
cr.gif">,a = 12.7214(5) Å, b = 14.7402(7) Å, c = 22.6724(9) Å, chars/alpha.gif" BORDER=0> = 71.550(3)
, chars/beta2.gif" BORDER=0 ALIGN="middle"> = 84.019(3), chars/gamma.gif" BORDER=0 > = 74.383(3), V =3883.2(3) Å3, Z = 1. The solution studies, including 183W NMR spectroscopy and luminescence lifetime measurements,show that the molecules dissociate in solution to form monomeric [Ln(H2O)4(chars/alpha.gif" BORDER=0>-2-P2W17O61)]7- species.
chars/alpha.gif" BORDER=0>-2-P2W17O61)]7- moieties connected through twoEu-O-W bonds, one from each polyoxometalate unit. An inversion center relates the two polyoxometalate units.The Eu(III) ion is substituted for a [WO]4+ unit in the "cap" region of the tungsten-oxygen framework of the parentWells-Dawson ion. The point group of the dimeric molecule is Ci. The extended structure is composed of the[Eu(H2O)3(chars/alpha.gif" BORDER=0>-2-P2W17O61)]214- anions linked together by surface-bound potassium cations. The space group is Pcr.gif">,a = 12.7214(5) Å, b = 14.7402(7) Å, c = 22.6724(9) Å, chars/alpha.gif" BORDER=0> = 71.550(3), chars/beta2.gif" BORDER=0 ALIGN="middle"> = 84.019(3), chars/gamma.gif" BORDER=0 > = 74.383(3), V =3883.2(3) Å3, Z = 1. The solution studies, including 183W NMR spectroscopy and luminescence lifetime measurements,show that the molecules dissociate in solution to form monomeric [Ln(H2O)4(chars/alpha.gif" BORDER=0>-2-P2W17O61)]7- species.