In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2008, No. 21 ( 2008-07), p. 3286-3294
Abstract:
The mixed addenda isopolyanion, [N(CH 3 ) 4 ] 2 Na 2 [ cis ‐Nb 2 W 4 O 19 ] · 18H 2 O, reacts with Cu(NO 3 ) 2 in water and in the presence of NH 2 CH 2 CH 2 NH 2 (en) or NH 4 OH at 60 °C to yield a phase that is decorated {[Cu(en) 2 (H 2 O)] 2 [Nb 2 W 4 O 19 ] · 2H 2 O ( 1 )} or charge‐balanced {[Cu(NH 3 ) 4 (H 2 O)] 2 [Nb 2 W 4 O 19 ] · 8H 2 O ( 2 )}, respectively, by (amine)copper complexes. The prolonged heating at 95 °C of [N(CH 3 ) 4 ] 6 [Nb 10 O 28 ] · 6H 2 O, [N(CH 3 ) 4 ] 2 Na 2 [ cis ‐Nb 2 W 4 O 19 ] · 18H 2 O, or Na 4 K 2 [ cis ‐Nb 4 W 2 O 19 ] · 12H 2 O and Cu(NO 3 ) 2 in a mixed water/amine [en or NH 2 CH 2 CH 2 CH 2 NH 2 (dap)] solution results in the formation of two‐dimensional materials with alternate layers of (amine)copper complexes linking Lindqvist [Nb 6– x W x O 19 ] (8– x )– ( x = 0–4) clusters. These phasesinclude: [Cu(dap) 2 ] 3 [Nb 4 W 2 O 19 ] · 7H 2 O ( 3 ), [Cu(dap) 2 ] 3 [H 2 Nb 6 O 19 ] · 6H 2 O ( 4 ), [Cu(dap) 2 ] 3 [Nb 3 W 3 O 19 ] · Cl · 6H 2 O ( 5 ), and [Cu(en) 2 ] 3 [Nb 4 W 2 O 19 ] · 6H 2 O ( 6 ). Complexes 4 and 5 result from the decomposition of [Nb 10 O 28 ] 6– and [ cis ‐Nb 2 W 4 O 19 ] 4– to [H 2 Nb 6 O 19 ] 6– and [ fac ‐Nb 3 W 3 O 19 ] 5– , respectively, in alkaline solution. Complex 5 contains an extra‐framework site that is occupied by Cl – , but this site is occupied by a water molecule in 3 and is vacant in structures 4 and 6 . The results of this study suggest that charge density, cluster charge and symmetry, and cluster‐cation pairing are all important parameters in the incorporation of d‐electron metals onto the surfaces of [Nb 6– x W x O 19 ] (8– x )– ( x = 0–4) clusters or into the frameworks of Lindqvist‐based complex materials.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2008:21
DOI:
10.1002/ejic.200800415
Language:
English
Publisher:
Wiley
Publication Date:
2008
detail.hit.zdb_id:
1475009-0
detail.hit.zdb_id:
1409951-2
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