ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2007, Vol. 33, No. 1, pp. 68–78. © Pleiades Publishing, Ltd., 2007. Original Russian Text © V.V. Semenov, N.F. Cherepennikova, I.S. Grigor’ev, L.G. Klapshina, O.V. Kuznetsova, M.A. Lopatin, B.A. Bushuk, S.B. Bushuk, Yu.A. Kal’vinkovskaya, W.E. Douglas, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 1, pp. 70–80. 68 β-Diketones belong to one of a few classes of organic compounds that can impart a whole set of use- ful properties such as volatility, stability in air, and solubility in organic solvents to derivatives of rare- earth metals. β-Diketones are actively used as analyt- ical reagents in photometry [1]. Numerous investiga- tions [2–5] have been aimed at obtaining stable vola- tile coordination compounds of transition and rare- earth metals from β-diketonates for subsequent use for separation of rare-earth metals and film formation by chemical vapor deposition (CVD). Methods devel- oped recently in [6, 7] for the synthesis of silylated derivatives R 3 SiC(O)CH 2 C(O)R' allowed one to obtain the corresponding copper complexes that pos- sess all the characteristics required for CVD pro- cesses. Oligosiloxanes [8] and metal oligosiloxanes [9] containing β-diketonate fragments have been reported. Chloro(methyl)silanes Me 2 SiHCl and MeHSiCl 2 have been employed in [10] for silylation of unsaturated beryllium and aluminum chelates. Sil- icon-containing acetylacetone Et 3 SiCH 2 C[C(O)CH 3 ] 2 has been obtained in [11] from Et 3 SiCH 2 Br and potas- sium acetylacetonate. Here we used a β-diketone containing the functional triethoxysilylpropyl group in position 3 for the synthe- sis of europium(III), terbium(III), and ytterbium(III) complexes. The tendency of this group toward hydrol- ysis made it possible to use sol–gel processes for the formation of transparent films. RESULTS AND DISCUSSION 3-(3'-Triethoxysilylpropyl)pentane-2,4-dione (I) was prepared by silylation of 3-allylpentane-2,4-dione with triethoxysilane in the presence of Speier’s catalyst: Europium, Terbium, and Ytterbium 3-(3'-Triethoxysilylpropyl)pentane-2,4-Dionates. Synthesis and the Formation of Luminescent Sol–Gel Films V. V. Semenov a , N. F. Cherepennikova a , I. S. Grigor’ev a , L. G. Klapshina a , O. V. Kuznetsova a , M. A. Lopatin a , B. A. Bushuk b , S. B. Bushuk b , Yu. A. Kal’vinkovskaya b , and W. E. Douglas c a Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, ul. Tropinina 49, Nizhni Novgorod, 603950 Russia b Stepanov Institute of Physics, Belarussian Academy of Sciences, Minsk, 220072 Belarus c University II, Montpellier, France Received February 22, 2006 Abstract—3-(3'-Triethoxysilylpropyl)pentane-2,4-dione, (EtO) 3 SiCH 2 CH 2 CH 2 C[–C(O)CH 3 ] 2 (I), was synthe- sized from 3-allylpentane-2,4-dione, CH 2 = CH–CH 2 –C[–C(O)CH 3 ] 2 , and triethoxysilane, (EtO) 3 SiH, in the presence of Speier’s catalyst. The silylation occurred mainly at the terminal C atom of the allyl group. The cor- responding europium(III), terbium(III), and ytterbium(III) β-diketonates were synthesized from compound I and appropriate metal isopropoxides and used to obtain transparent sol–gel films containing Eu 3+ , Tb 3+ , and Yb 3+ cations. The film formation was studied by IR spectroscopy. It was found that moisture causes not only the hydrolysis and condensation of triethoxysilyl groups but also the hydration of the cation of the rare-earth metal. When the terbium complex was excited at the wavelength of one of the two peaks (230 and 308 nm) in the excitation spectrum, the cation fluoresced intensely at 491, 547, 585, and 623 nm due to the transitions 5 D 4 7 F 6 , 5 D 4 7 F 5 , 5 D 4 7 F 4 , and 5 D 4 7 F 3 , respectively. All these bands were narrow, the band at 547 nm being most intense. No emission from the organosilicon matrix at 440 nm was observed. The emis- sion spectra of Eu 3+ -containing films showed, along with the bands at 593, 618, 667, and 700 nm due to the emission from the cation ( 5 D 0 7 F 1 , 5 D 0 7 F 2 , 5 D 0 7 F 3 , and 5 D 0 7 F 4 transitions, respectively), an intense band at 491 nm due to the emission from the matrix. DOI: 10.1134/S1070328407010101