Trivalent lanthanide lacunary phosphomolybdate complexes: A structural and spectroscopic study across the series [Ln(PMo11O39) 2]11-

Roy Copping; Andrew J. Gaunt; Iain May; Mark J. Sarsfield; David Collison; Madeleine Helliwell; Iain S. Denniss; David C. Apperley

doi:10.1039/b500408j

Trivalent lanthanide lacunary phosphomolybdate complexes: A structural and spectroscopic study across the series [Ln(PMo₁₁O₃₉) ₂]^11-

Roy Copping, Andrew J. Gaunt, Iain May, Mark J. Sarsfield, David Collison, Madeleine Helliwell, Iain S. Denniss, David C. Apperley

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Abstract

We report the syntheses and crystal structures of (NH₄) ₁₁[Ln^III(PMo₁₁O₃₉) ₂]·xH₂O (where Ln = every trivalent lanthanide cation except promethium) in which two lacunary [PMo₁₁O ₃₉]^7- anions sandwich an 8-coordinate Ln^III cation to yield the complex anion, [Ln^III(PMo₁₁O ₃₉)₂]^11-. The 14 salts crystallise in two different space groups, C2/c or P1̄, but the Ln^III containing anions are isostructural across the whole series, a very rare example of such a complete study. Solid state and solution ³¹P NMR, Raman and IR spectroscopies have been used to prove the stability of [Ln(PMo ₁₁O₃₉)₂]^11- in aqueous solution. As expected, the Ln^III cation contracts across the series and the Ln-O bond distances decrease uniformly. Interestingly, the splitting in the V _P-O mode within the [PMo₁₁O₃₉]^7- unit increases uniformly across the series, which we attribute to the stronger interaction with the smaller, higher charge density Ln^III cation as the series is traversed. For the ³¹P NMR measurements a direct comparison of Lanthanide Induced (paramagnetic) Shift could be made with the analogous [P(W₁₁O₃₉)₂]^11- complexes.

Original language	English
Pages (from-to)	1256-1262
Number of pages	7
Journal	Dalton Transactions
Issue number	7
DOIs	https://doi.org/10.1039/b500408j
State	Published - Apr 7 2005
Externally published	Yes

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@article{6252e6a6e6814416b0f61ca454cccc3e,

title = "Trivalent lanthanide lacunary phosphomolybdate complexes: A structural and spectroscopic study across the series [Ln(PMo11O39) 2]11-",

abstract = "We report the syntheses and crystal structures of (NH4) 11[LnIII(PMo11O39) 2]·xH2O (where Ln = every trivalent lanthanide cation except promethium) in which two lacunary [PMo11O 39]7- anions sandwich an 8-coordinate LnIII cation to yield the complex anion, [LnIII(PMo11O 39)2]11-. The 14 salts crystallise in two different space groups, C2/c or P{\=1}, but the LnIII containing anions are isostructural across the whole series, a very rare example of such a complete study. Solid state and solution 31P NMR, Raman and IR spectroscopies have been used to prove the stability of [Ln(PMo 11O39)2]11- in aqueous solution. As expected, the LnIII cation contracts across the series and the Ln-O bond distances decrease uniformly. Interestingly, the splitting in the V P-O mode within the [PMo11O39]7- unit increases uniformly across the series, which we attribute to the stronger interaction with the smaller, higher charge density LnIII cation as the series is traversed. For the 31P NMR measurements a direct comparison of Lanthanide Induced (paramagnetic) Shift could be made with the analogous [P(W11O39)2]11- complexes.",

author = "Roy Copping and Gaunt, {Andrew J.} and Iain May and Sarsfield, {Mark J.} and David Collison and Madeleine Helliwell and Denniss, {Iain S.} and Apperley, {David C.}",

year = "2005",

month = apr,

day = "7",

doi = "10.1039/b500408j",

language = "English",

pages = "1256--1262",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "7",

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T1 - Trivalent lanthanide lacunary phosphomolybdate complexes

T2 - A structural and spectroscopic study across the series [Ln(PMo11O39) 2]11-

AU - Copping, Roy

AU - Gaunt, Andrew J.

AU - May, Iain

AU - Sarsfield, Mark J.

AU - Collison, David

AU - Helliwell, Madeleine

AU - Denniss, Iain S.

AU - Apperley, David C.

PY - 2005/4/7

Y1 - 2005/4/7

N2 - We report the syntheses and crystal structures of (NH4) 11[LnIII(PMo11O39) 2]·xH2O (where Ln = every trivalent lanthanide cation except promethium) in which two lacunary [PMo11O 39]7- anions sandwich an 8-coordinate LnIII cation to yield the complex anion, [LnIII(PMo11O 39)2]11-. The 14 salts crystallise in two different space groups, C2/c or P1̄, but the LnIII containing anions are isostructural across the whole series, a very rare example of such a complete study. Solid state and solution 31P NMR, Raman and IR spectroscopies have been used to prove the stability of [Ln(PMo 11O39)2]11- in aqueous solution. As expected, the LnIII cation contracts across the series and the Ln-O bond distances decrease uniformly. Interestingly, the splitting in the V P-O mode within the [PMo11O39]7- unit increases uniformly across the series, which we attribute to the stronger interaction with the smaller, higher charge density LnIII cation as the series is traversed. For the 31P NMR measurements a direct comparison of Lanthanide Induced (paramagnetic) Shift could be made with the analogous [P(W11O39)2]11- complexes.

AB - We report the syntheses and crystal structures of (NH4) 11[LnIII(PMo11O39) 2]·xH2O (where Ln = every trivalent lanthanide cation except promethium) in which two lacunary [PMo11O 39]7- anions sandwich an 8-coordinate LnIII cation to yield the complex anion, [LnIII(PMo11O 39)2]11-. The 14 salts crystallise in two different space groups, C2/c or P1̄, but the LnIII containing anions are isostructural across the whole series, a very rare example of such a complete study. Solid state and solution 31P NMR, Raman and IR spectroscopies have been used to prove the stability of [Ln(PMo 11O39)2]11- in aqueous solution. As expected, the LnIII cation contracts across the series and the Ln-O bond distances decrease uniformly. Interestingly, the splitting in the V P-O mode within the [PMo11O39]7- unit increases uniformly across the series, which we attribute to the stronger interaction with the smaller, higher charge density LnIII cation as the series is traversed. For the 31P NMR measurements a direct comparison of Lanthanide Induced (paramagnetic) Shift could be made with the analogous [P(W11O39)2]11- complexes.

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U2 - 10.1039/b500408j

DO - 10.1039/b500408j

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SN - 1477-9226

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EP - 1262

JO - Dalton Transactions

JF - Dalton Transactions

IS - 7

ER -

Trivalent lanthanide lacunary phosphomolybdate complexes: A structural and spectroscopic study across the series [Ln(PMo₁₁O₃₉) ₂]^11-

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