Synthesis and characterization of two new photochromic inorganic-organic hybrid materials based on Keggin-type polyoxometalates

Abstract

Two new photochromic inorganic-organic hybrid materials formed from Keggin-type polyoxometalates(POMs) and metronidazole (C₆H₉N₃O₃, MNZ), formulated as H₃PMo₁₂O₄₀·3MNZ·3H₂O(1) and H₃PW₁₂O₄₀·3MNZ·3H₂O(2), were synthesized and characterized by elemental analysis, IR spectra, electronic spectra, electron spin resonance (ESR) spectra and thermogravi-metry-differential thermal analysis (TG-DTA). Reflectance spectra show the presence of weak intermolecular charge transfer between the organic and inorganic moieties in the solid state. The photochromic properties were studied by solid diffuse reflectance spectra and ESR spectra, and the photochromic reactions were found to exhibit first-order kinetics. TG-DTA showed that two hybrid materials have similar thermal behavior.

Keywords

polyoxometalate / metronidazole / hybrid material / photochromism / kinetics

References

[1] Pope M. T. Heteropoly and Isopoly Oxometalates[M], 1983. Berlin: Springer. 32

[2] Wang E. B., Hu C. W., Xu L. Concise Polyoxometalates[M], 1998. Beijing: Chemical Industry. 28

[3] Niu J. Y., You X. Z., Duan C. Y., . A Novel Optical Complex between an Organic Substrate and a Polyoxometalate Crystal and Molecular Structure of α-H₄SiW₁₂O₄₀·4HMPA·2H₂O[J]. Inorg. Chem., 1996, 14: 4 211-4 217.

[4] Bi L. H., Wang E. B., Xu L., . Synthesis, Properties and Crystal Structure of Some Polyoxometallates Containing the tris(hydroxymethyl)aminomethane Cation[J]. Inorg. Chim. Acta, 2000, 305: 163-171.

[5] Gamelas J. A. F., Cavaleiro A. M. V., Gomes E. D. M., . Synthesis, Properties and Photochromism of Novel Charge Transfer Compounds with Keggin Anions and Protonated 2,2′-Biquinoline[J]. Polyhedron, 2002, 21(25/26): 2 537-2 545.

[6] Zhang H. Y., Xu L., Wang E. B., . Photochromic Behavior and Luminescent Properties of Novel Hybrid Organic-inorganic Film Doped with Preyssler’s Heteropoly Acid H₁₂[EuP₅W₃₀O₁₁₀] and Polyvinylpyrrolidone[J]. Mater. Lett., 2003, 57(8): 1 417-1 422.

[7] Jin S. R., Zhang L. M., Liu S. Z., . Hydrothermal Synthesis and Characterization of Inorganic/organic Hybrid Complex Containing Tungstophosphate[J]. J. Wuhan University of Technology-Mater. Sci. Ed., 2004, 19(4): 21-22.

[8] Huang Y., Pan Q. Y., Dong X. W., . Synthesis and Photochromism of a Novel Organic-inorganic Hybrid Film Embedded with Polyoxomatalates[J]. Mater. Chem. Physi., 2006, 97: 431-436.

[9] Han Z. B., Wang E. B., Luan G. Y., . Synthesis, Properties and Structural Characterization of an Intermolecular Photosensitive Complex: (HGly-Gly)₃PMo₁₂O₄₀·4H₂O[J]. J. Mater. Chem., 2002, 12: 1 169-1 173.

[10] Zhang T. R., Feng W., Lu R., . Synthesis and Characterization of Polymetalate Based Photochromic Inorgani-organic Nanocomposites[J]. Thin Solid Films, 2002, 402: 237-241.

[11] Feng W., Zhang T. R., Liu Y., . Sonochemical Preparation of Photochromic Nanocomposite Thin Film Based on Polyoxometalates well Dispersed in Polyacrylamide[J]. J. Solid State Chem., 2002, 169: 1-5.

[12] Zhang L. J., Wei Y. G., Wang C. C., . Hexatungstate Subunit as Building Block in the Hydrothermal Synthesis of Organic-inorganic Hybrid Materials: Synthesis, Structure and Optical Properties of Co₂(bpy)₆(W₆O₁₉)₂(bpy=4,4′-bipyridine)[J]. J. Solid State Chem., 2004, 177: 3 433-3 438.

[13] Feng W., Ding Y. S., Liu Y., . The Photochromic Process of Polyoxometalate-based Nanocomposite Thin Film by in Situ AFM and Spectroscopy[J]. Mater. Chem. Physi., 2006, 98: 347-352.

[14] Coué V., Dessapt R., Bujoli-Doeuff M., . Synthesis and Characterization of Two New Photochromic Organic-inorganic Hybrid Materials Based on Isopolyoxomolybdate (HDBU)₃(NH₄) [β-Mo₈O₂₆]·H₂O and (HDBU)₄[δ-Mo₈O₂₆][J]. J. Solid State Chem., 2006, 179: 3 615-3 627.

[15] Sworakowski J., Janus K., Nešpůrek S. Kinetics of Photochromic Reactions in Condensed Phases[J]. Adv. Coll. Int. Sci., 2005, 116(1–3): 97-110.

[16] Ku Z. J., Liu S. Z., Wang Q. R., . Study on the Synthesis and Photochromism of (QLH)₆[As₂Mo₁₈O₆₂]·3QL·1.5EtOH[J]. J. Hubei University-Nat. Sci. Ed., 1998, 20(2): 157-160.

[17] Liu S. Z., Ku Z. J., Wang Z. Synthesis and Characterization of a New Charge-transfer Complex[J]. Chin. J. Inorg. Chem., 1999, 15(2): 223-266.

[18] Liu S. Z., Wang Z., Ku Z. J., . Synthesis, Structure and Properties of Charge-transfer Complexes Containing Tungstop hosphoric(arsenic) Heteropolyacid with Dawson Structure[J]. Chin. J. Inorg. Chem., 1999, 15(5): 652-656.

[19] J A F Gamelas, F M Santos, V Felix, et al. Novel Charge Transfer Supramolecular Assemblies with Keggin Anions and 2-Amino-5-nitropyridine[J]. J. Chem. Soc., Dalton Trans., 2006:1 197–1 203

[20] Galván T. N., Bernés S., Castillo Blum S. E., . Supramolecular Structures of Metronidazole and Its Copper(II), Cobalt(II) and Zinc(II) Coordination Compounds[J]. J. Inorg. Biochem., 2002, 91(1): 339-348.

[21] Niu J. Y., Han Q. X., Wang J. P. Synthesis, Crystal Structure and Properties of Novel Composite Complex: [La(NMP)₄(H₂O)₄][HSiMO₁₂O₄₀]·2NMP·H₂O[J]. J. Coord. Chem., 2003, 56(11): 1 003-1 012.

[22] Kawato T., Koyama H., Kanatomi H., . Photoisomerization and Thermoisomerization I: Unusual Photochromism of N-(3,5-di-tert-butyl-salicylidene) Amines[J]. J. Photochem., 1985, 28(1): 103-110.

[23] Liu L., Jia D. Z., Ji Y. L., . Synthesis, Structure and Photochromic Properties of 4-Acylpyrazolone Derivants[J]. J. Photochem. Photobio., A: Chem., 2003, 154(2/3): 117-122.

[24] Fodor A., Ghizdavu L., Şuteu A., . Synthesis and TG/DTA Study on Two New Metallo(VI)-ars-enato(V) Heterpolyacids Containing Vanadium(V)[J]. J. Therm. Anal. Cal., 2004, 75: 153-158.