Synthesis and characterization of two new photochromic organic-inorganic hybrid materials based on isopolyoxomolybdate: (HDBU){sub 3}(NH{sub 4})[{beta}-Mo{sub 8}O{sub 26}].H{sub 2}O and (HDBU){sub 4}[{delta}-Mo{sub 8}O{sub 26}]
- Institut des Materiaux Jean ROUXEL, UMR 6502 CNRS-Universite de Nantes, Laboratoire de Chimie des Solides, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3 (France)
Two new organic-inorganic hybrid compounds of molybdenum(VI) (HDBU){sub 3}(NH{sub 4})[{beta}-Mo{sub 8}O{sub 26}].H{sub 2}O 1 and (HDBU){sub 4}[{delta}-Mo{sub 8}O{sub 26}] 2 have been synthesized and characterized by elemental analyses, FT-IR and UV-vis spectroscopies, and single-crystal X-ray diffraction (at 293 and 100K, respectively). Compound 1 is obtained at room temperature by adding 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) on aqueous molybdate solution at pH=5.7. Compound 2 is obtained hydrothermally from 1 (110 deg. C, 24h, autogenous pressure). Compound 1 crystallizes in the triclinic crystal system, space group P1-bar , with a=11.2492(9), b=14.1907(10), c=16.7498(10)A, {alpha}=80.993(4), {beta}=72.272(6), {gamma}=71.696(7){sup o}, V=2412.5(3)A{sup 3} at T=20 deg. C and Z=2. The refinement of the structure leads to a residual factor R=0.0697 for 10234 independent observed reflections [I/{sigma}(I)>=2] and 623 parameters. Compound 2 crystallizes in the triclinic crystal system, space group P1-bar , with a=11.3158(9), b=11.3773(8), c=13.2884(17)A, {alpha}=92.110(8), {beta}=112.127(9), {gamma}=117.581(7){sup o}, V=1357.4(3)A{sup 3} at T=-173{sup o}C and Z=2. The refinement of the structure leads to a residualtor R=0.0226 for 11812 independent observed reflections [I/{sigma}(I)>=2] and 354 parameters. The structure of 1 consists of {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} anions with HDBU{sup +} and NH{sub 4}{sup +} cations connected to the mineral parts by hydrogen bonds and the structure of 2 contains {delta}-[Mo{sub 8}O{sub 26}]{sup 4-} anions with HDBU{sup +} counter-cations. Both the thermal and chemical isomerizations of the two [Mo{sub 8}O{sub 26}]{sup 4-} isomers are highlighted and discussed. Photochromic behaviors of compounds 1 and 2 are also reported.
- OSTI ID:
- 20900901
- Journal Information:
- Journal of Solid State Chemistry, Vol. 179, Issue 12; Other Information: DOI: 10.1016/j.jssc.2006.07.031; PII: S0022-4596(06)00425-7; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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