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Solid-State Structural Characterization of a Rigid Framework of Lacunary Heteropolyniobates

Supporting Info

May Nyman,*^† Aaron J. Celestian,^‡ John B. Parise,^‡ Gregory P. Holland,^† and Todd M. Alam^†

Sandia National Laboratories, P.O. Box 5800, Albuquerque, New Mexico 87185, and Center for Environmental and Molecular Sciences, Department of Geosciences, State University of New York, Stony Brook, New York 11794-2100

Inorg. Chem., 2006, 45 (3), pp 1043–1052

DOI: 10.1021/ic051155g

Publication Date (Web): January 12, 2006

To whom correspondence should be addressed. E-mail: mdnyman@ sandia.gov.

†

Sandia National Laboratories.

‡

State University of New York.

Abstract

In our ongoing investigations of heteropolyniobate chemistry, a phase featuring decorated, A-type trivacant α-Keggin ions linked by their charge-balancing sodium cations has been isolated and structurally characterized. This is the first heteropolyniobate reported that has a true lacunary structure type. Na₁₅[(PO₂)₃PNb₉O₃₄]·22H₂O (1) [triclinic space group P (No. 2); a = 12.242 (2) Å, b = 12.291 (3) Å, c = 22.056 (4) Å; α = 93.12 (3)°, β = 99.78 (3)°, γ = 119.84 (3)°; Z = 4, V = 2799.2 (10) Å³] is composed of bilayers of the heteropolyanions alternating with layers of hydrated Na⁺ cations. Sodium cations also bridge the clusters within their layers through Na−O_t−Nb, Na−O_b−Nb₂, and Na−O_t−P bonds (t = terminal and b = bridging). This phase is poorly soluble in water, suggesting that it is more characteristic of a framework of linked heteropolyanions rather than a water-soluble heteropolyanion salt. Two-dimensional solid-state ²³Na multiple-quantum magic angle spinning (MAS) NMR of 1 reveals five distinctive chemical and structural environments for sodium, which agrees with the crystallographic data. The ²³Na and ¹H MAS NMR studies further illustrate the rigid and immobile nature of this framework of cations and anions.

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Published In Issue February 06, 2006
Received July 11, 2005

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Article

Solid-State Structural Characterization of a Rigid Framework of Lacunary Heteropolyniobates