Hostname: page-component-cd9895bd7-jn8rn Total loading time: 0 Render date: 2024-12-27T23:43:48.188Z Has data issue: false hasContentIssue false
  • English
  • Français

An unusual way to luminescent terbium molecular-level hybrid materials: Modified methyl benzoic acid covalently bonded with silica as a bridge

Published online by Cambridge University Press:  01 March 2005

Qianming Wang  and
Bing Yan
Qianming Wang
Affiliation:
Department of Chemistry, Tongji University, Shanghai 200092, People's Republic of China
Bing Yan*
Affiliation:
Department of Chemistry, Tongji University, Shanghai 200092, People's Republic of China
*
a)Address all correspondence to this author. e-mail: byan@tongji.edu.cn
Get access

Abstract

The syntheses of modified ortho or meta methylbenzoic acid by (3-aminopropyl)triethoxysilane and the preparation of their corresponding organic–inorganic molecular-based hybrid material with the two components equipped with covalent bonds are described. The organic part is a derivative of methyl benzoic acid, which is used to coordinate to Tb3+ and further introduced into silica matrices by Si–O bonds after hydrolysis and polycondensation processes. The Judd–Ofelt theory proves that covalency increases along with increasing reciprocal energy difference between the 4fN and 4fN−15d1 configurations. Ultraviolet absorption, phosphorescence spectra, and luminescence spectra were applied to characterize the photophysical properties of the obtained hybrid material, and the above spectroscopic data reveal that the triplet energy of modified methyl benzoic acid matches with the emissive energy level of Tb3+. In this way, the intramolecular energy transfer process took place within these molecular-based hybrids, and strong green emission of Tb3+ was obtained.

Keywords

LuminescenceMorphologySol-gel
Type
Articles
Information
Journal of Materials Research , Volume 20 , Issue 3 , March 2005 , pp. 592 - 598
Copyright
Copyright © Materials Research Society 2005

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1.Molina, C., Dahmouche, K. and Santilli, C.V.: Structure and luminescence of Eu3+-doped class I siloxane-poly(ethylene glycol). Hybrids. Chem. Mater. 13, 2818 (2001).CrossRefGoogle Scholar
2.Suratwala, T., Gardlund, Z., Davidson, K. and Uhlmann, D.R.: Silylated coumarin dyes in sol-gel hosts. 1. Structure and environmental factors on fluorescent properties. Chem. Mater. 10, 190 (1998).CrossRefGoogle Scholar
3.Matthews, L.R. and Knobbe, E.T.: Luminescence behavior of europium complexes in sol-gel derived host materials. Chem. Mater. 5, 1697 (1993).CrossRefGoogle Scholar
4.Yan, B. and Zhang, H.J.: Sol-gel preparation and luminescence of silica gel/polymer hybrid material incorporated with europium complex. J. Adv. Mater. 33, 39 (2001).Google Scholar
5.Lebeau, B., Fowler, C.E. and Hall, S.R.: Transparent thin films and monoliths prepared from dye-functionalized ordered silica mesostructures. J. Mater. Chem. 9, 2279 (1999).CrossRefGoogle Scholar
6.Innocenzi, P., Kozuka, P. and Yoko, T.J.: Fluorescence properties of the Ru(bpy)32+ complex incorporated in sol-gel-derived silica coating films. J. Phys. Chem. B 101, 2285 (1997).CrossRefGoogle Scholar
7.Mstsui, K. and Momose, F.: Luminescence properties of Tris(2,2′-bipyridine)ruthenium(II) in sol-gel systems of SiO2. Chem. Mater. 9, 2588 (1997).Google Scholar
8.Maruszewski, K., Andrzejewski, D. and Strke, W.: Thermal sensor based on luminescence of Ru(bpy)2+3 entrapped in sol-gel glasses. J. Lumin. 72–4, 226 (1997).CrossRefGoogle Scholar
9.Murtagh, M., Kwon, H.C. and Shahriari, M.R.: Luminescence probing of various sol-gel hosts with a Ru(II) complex and the practical ramifications for oxygen-sensing applications. J. Mater. Res. 13, 3326 (1998).CrossRefGoogle Scholar
10.Tanner, P.A., Yan, B. and Zhang, H-J.: Preparation and luminescence properties of sol-gel hybrid materials incorporated with europium complexes. J. Mater. Sci. 35, 4325 (2000).CrossRefGoogle Scholar
11.Zhang, H-J., Fu, L-S., Wang, S-B., Meng, Q-G., Yang, K-Y. and Ni, J-Z.: Luminescence characteristics of europium and terbium complexes with 1,10-phenanthroline in-situ synthesized in a silica matrix by a two-step sol–gel process. Mater. Lett. 38, 260 (1999).CrossRefGoogle Scholar
12.Gracia, J., Mondragon, M.A. and Tellez, C.: Blue emission in tetraethoxysilane and silica gels. Mater. Chem. Phys. 41, 15 (1995).CrossRefGoogle Scholar
13.Yan, B., Zhang, H-J., Wang, S-B. and Ni, J-Z.: Luminescence properties of the ternary rare earth complexes with β-diketones and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method. Mater. Chem. Phys. 51, 92 (1997).CrossRefGoogle Scholar
14.Sanchez, C. and Ribot, F.: Design of hybrid inorganic-organic materials synthesized via sol-gel chemistry. New J. Chem. 18, 1007 (1994).Google Scholar
15.Li, H-R., Lin, J., Zhang, H-J. and Fu, L-S.: Preparation and luminescence properties of hybrid materials containing europium(III) complexes covalently bonded to a silica matrix. Chem. Mater. 14, 3651 (2002).CrossRefGoogle Scholar
16.Li, H-R., Lin, J., Zhang, H-J. and Fu, L-S.: Novel covalently bonded hybrid materials of europium(terbium) complexes with silica. Chem. Commun. 1212(2001).Google Scholar
17.Dong, D-W., Jiang, S-C., Men, Y-F., Ji, X-L. and Jiang, B-Z.: Nanostructured hybrid organic-inorganic lanthanide complex films produced in situ via a sol-gel approach. Adv. Mater. 12, 646 (2000).3.0.CO;2-W>CrossRefGoogle Scholar
18.Li, H-R., Fu, L-S. and Zhang, H-J.: Luminescence properties of transparent hybrid thin film covalently linked with lanthanide complexes. Thin Solid Films 416, 197 (2002).CrossRefGoogle Scholar
19.Li, H-R., Lin, J., Fu, L-S., Guo, J-F., Meng, Q-G., Liu, F-Y. and Zhang, H.J.: Phenanthroline-functionalized MCM-41 doped with Europium ions. Microporous Mesoporous Mater. 55, 103 (2002).CrossRefGoogle Scholar
20.Liu, F-Y., Fu, L-S., Wang, J., Liu, Z., Li, H-R. and Zhang, H-J.: Luminescent hybrid films obtained by covalent grafting of terbium complex to silica network. Thin Solid Films 419, 178 (2002).CrossRefGoogle Scholar
21.Binnemans, K., Lenaerts, P., Driesen, K. and Gorller-Walrand, C.: A luminescent tris(2-thenoyltrifluoroacetonato)europium(III) complex covalently linked to a 1,10-phenanthroline-functionalised sol-gel glass. J. Mater. Chem. 14, 291 (2004).CrossRefGoogle Scholar
22.Franville, A.C., Zambon, D. and Mahiou, R.: Luminescence behavior of sol-gel-derived hybrid materials resulting from covalent grafting of a chromophore unit to different organically modified alkoxysilanes. Chem. Mater. 12, 428 (2000).CrossRefGoogle Scholar
23.Minoofar, P.N., Hernandez, R., Chia, S., Dunn, B., Zink, J.I. and Franville, A.C.: Placement and characterization of pairs of luminescent molecules in spatially separated regions of nanostructured thin films. J. Am. Chem. Soc. 124, 14388 (2002).CrossRefGoogle ScholarPubMed
24.Wang, Q-M. and Yan, B.: Novel luminescent molecular-based hybrid organic–inorganic terbium complex covalently bonded materials via sol-gel process. Inorg. Chem. Commun. 7, 747 (2004).CrossRefGoogle Scholar
25.Wang, Q-M. and Yan, B.: Novel luminescent terbium molecular-based hybrids with modified meta-aminobenzoic acid covalently bonded with silica. J. Mater. Chem. 14, 2450 (2004).CrossRefGoogle Scholar
26.Liu, F-Y., Fu, L-S. and Zhang, H-J.: Luminescent film with terbium-complex-bridged polysilsesquioxanes. New J. Chem. 27, 233 (2003).CrossRefGoogle Scholar
27.Sato, S. and Wada, M.: Relations between intramolecular energy transfer efficiencies and triplet state energies in rare earth βdiketone chelates. Bull. Chem. Soc. Jap. 43, 1955 (1970).CrossRefGoogle Scholar
28.Yang, Y-S., Gong, M-L., Li, Y-Y., Lei, H.Y. and Wu, Y-L.: Effects of the structure of ligands and their Ln3+ complexes on the luminescence of the central Ln3+ ions. J. Alloys Compd. 207/208, 112 (1994).CrossRefGoogle Scholar
29.Yan, B., Zhang, H-J., Wang, S-B. and Ni, J-Z.: The photophysical properties of some binary and ternary complexes of rare earth with aminobenzoic acids and 1,10-phenanthroline. Monatsh. Chem. 129, 151 (1998).Google Scholar
30.Yan, B., Zhang, H-J., Wang, S-B. and Ni, J-Z.: Luminescence properties of rare-earth (Eu3+ and Tb3+) complexes with para aminobenzoic acid and 1,10-phenanthroline incorporated into a silica matrix by sol-gel method. Mater. Res. Bull. 33, 1517 (1998).CrossRefGoogle Scholar
31.Zhang, H-J., Yan, B., Wang, S-B. and Ni, J-Z.: The photophysical properties of binary and ternary complexes of rare earths with conjugated carboxylic acids and 1,10-phenanthroline. J. Photochem. Photobiol. A 109, 223 (1997).CrossRefGoogle Scholar
32.Yan, B., Zhang, H-J., Wang, S-B. and Ni, J-Z.: Spectroscopic study of luminescence and intramolecular energy transfer of binary and ternary rare earth complexes with aromatic carboxylic acids and 1,10-phenanthroline. Spectrosc. Lett. 31, 603 (1998).Google Scholar
33.Judd, B.R.: Optical absorption intensities of rare-earth ions. Phys. Rev. 127, 750 (1962).CrossRefGoogle Scholar
34.Ofelt, G.S.: Intensities of crystal spectra of rare-earth ions. J. Chem. Phys. 37, 511 (1962).CrossRefGoogle Scholar
35.Ebendorff-Heidepriem, H.: Tb3+f–d absorption as indicator of the effect of covalency on the Judd–Ofelt Ω2 parameter in glasses. J. Non-Cryst. Solids 248, 247 (1999).CrossRefGoogle Scholar
36.Xu, S-Q., Yang, Z-M., Dai, S-X., Yang, J-H., Hu, L-L. and Jiang, Z-H.: Spectral properties and thermal stability of Er3+-doped oxyfluoride silicate glasses for broadband optical amplifier. J. Alloys Compd. 361, 313 (2003).CrossRefGoogle Scholar
37.Huang, Y-L., Feng, Z., Xu, H., Zhao, G-J., Huang, G-S. and Li, S.G.: Growth and spectra properties of Nd3+-doped PbWO4 single crystal. Solid State Commun. 127, 1 (2003).CrossRefGoogle Scholar
38.Ma, J-F., Jin, Z-S. and Ni, J-Z.: Syntheses, characterization and crystal structure of the complexes of rare earth with m-methylbenzoic acid. Acta Chim. Sin. 51, 265 (1993).Google Scholar