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Two hexa-TM-containing (TM = Co 2+ and Ni 2+ ) {P 2 W 12 }-based trimeric tungstophosphates

Two hexa-TM-containing (TM = Co 2+ and Ni 2+ ) {P 2 W 12 }-based trimeric tungstophosphates Reactions of hexavacant polyoxotungstates (H 2 P 2 W 12 O 48 ) 12− ({P 2 W 12 }) with transition-metal (TM), and alkali-metal ions lead to the isolation of two hexa-TM-containing polyoxotungstates Na 15 (Na 3 ⊂{M(H 2 O) 4 } 6 {WO(H 2 O)} 3 (P 2 W 12 O 48 ) 3 )· x H 2 O (M = Co 2+ , x = 109 for 1 ; M = Ni 2+ , x = 110 for 2 ). Single-crystal X-ray diffraction analysis revealed that compounds 1 and 2 both crystallized in the orthorhombic system, space group Cmcm , with lattice constants a = 21.353(3) Å, b = 32.114(3) Å, c = 33.848(4) Å, for 1 ; a = 21.643(6) Å, b = 31.870(6) Å, c = 33.861(7) Å for 2 . Polyoxoanions (Na 3 ⊂{M(H 2 O) 4 } 6 {WO(H 2 O)} 3 (P 2 W 12 O 48 ) 3 ) 15− in 1 and 2 exhibit a crown-type structure composed of a ({WO(H 2 O)} 3 (P 2 W 12 O 48 ) 3 ) 18- (abbreviated as {P 6 W 39 }) shell encapsulating six TM ions and three Na + cations. Polyoxoanions 1 and 2 represent the first hexa-TM-containing {P 2 W 12 }-based trimeric POMs, which offer new examples with the potentially aqua-ligand-induced capability of “trapping” metal ions in the {P 6 W 39 } shell. Electrocatalytic studies show that compounds 1 and 2 display electrocatalytic activity to reduce nitrite. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Dalton Transactions Royal Society of Chemistry

Two hexa-TM-containing (TM = Co 2+ and Ni 2+ ) {P 2 W 12 }-based trimeric tungstophosphates

Dalton Transactions , Volume 39 (16) – Mar 11, 2010

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References (76)

Publisher
Royal Society of Chemistry
Copyright
This journal is © The Royal Society of Chemistry
ISSN
1477-9226
eISSN
1477-9234
DOI
10.1039/b921261b
pmid
20372712
Publisher site
See Article on Publisher Site

Abstract

Reactions of hexavacant polyoxotungstates (H 2 P 2 W 12 O 48 ) 12− ({P 2 W 12 }) with transition-metal (TM), and alkali-metal ions lead to the isolation of two hexa-TM-containing polyoxotungstates Na 15 (Na 3 ⊂{M(H 2 O) 4 } 6 {WO(H 2 O)} 3 (P 2 W 12 O 48 ) 3 )· x H 2 O (M = Co 2+ , x = 109 for 1 ; M = Ni 2+ , x = 110 for 2 ). Single-crystal X-ray diffraction analysis revealed that compounds 1 and 2 both crystallized in the orthorhombic system, space group Cmcm , with lattice constants a = 21.353(3) Å, b = 32.114(3) Å, c = 33.848(4) Å, for 1 ; a = 21.643(6) Å, b = 31.870(6) Å, c = 33.861(7) Å for 2 . Polyoxoanions (Na 3 ⊂{M(H 2 O) 4 } 6 {WO(H 2 O)} 3 (P 2 W 12 O 48 ) 3 ) 15− in 1 and 2 exhibit a crown-type structure composed of a ({WO(H 2 O)} 3 (P 2 W 12 O 48 ) 3 ) 18- (abbreviated as {P 6 W 39 }) shell encapsulating six TM ions and three Na + cations. Polyoxoanions 1 and 2 represent the first hexa-TM-containing {P 2 W 12 }-based trimeric POMs, which offer new examples with the potentially aqua-ligand-induced capability of “trapping” metal ions in the {P 6 W 39 } shell. Electrocatalytic studies show that compounds 1 and 2 display electrocatalytic activity to reduce nitrite.

Journal

Dalton TransactionsRoyal Society of Chemistry

Published: Mar 11, 2010

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