Kompleksy alkoholanów Ti(IV) i Zr(IV) z ligandami O-donorowymi. Synteza, charakterystyka strukturalna i zasotosowania

• Autorzy: Piszczek P.

Warianty tytułu

EN

Ti(IV) and Zr(IV) alkoxo complexes with O-donor ligands. Synthesis, structural characterization and applications

• Języki publikacji: PL

Abstrakty

EN

Extensive studies of complexes of titanium(IV) and zirconium(IV) alkoxides with O-donor ligands observed for the last few years are a result of their wide applications in nanomaterial technologies. Various physicochemical properties of TiO2 and ZrO2 including high reference factor (n = 2,616-2,903 TiO2), low absorption in visible range, photoluminescence, high dielectric constant (?TiO2 = 120 for rutile), high stability and chemical resistance have significant influence on their use. Thin metal oxide layers are prepared by vaporization and condensation methods [1], hydrolysis in the flame [2], vacuum deposition, sol-gel techniques, and also chemical vapor deposition (CVD). The last two methods are most often used to prepare high quality ceramic materials, thin metal oxide layers, organic-inorganic hybrid polymers, dopped materials (M2O/M'; M = Ti, Zr; M' = Cu, Ag, Au, Pt, Pd) as well as mesoporous materials [3-15]. In both techniques a very important role is played by precursors, which influence CVD process, and the structure of deposited layers. Ti(IV) and Zr(IV) alkoxides (M(OR)4) are usually used as CVD precursors of thin TiO2 and ZrO2 layers. However, high reactivity of M(OR)4 towards nucleophilic reagents, in particularly hydrolysis and condensation of metal alkoxides, lead to precipitation of oxo-polymers. In order to stabilize the alkoxo precursor, Ti(IV) and Zr(IV) complexes containing anionic bidendate groups, such as ?-diketones, carboxylates, alkylamides, sulfonates have been studied [14-17]. In the presented paper, the review of synthetic methods and structural characterization of the following type of complexes [M(OR)4-x(L)x] (M = Ti(IV), Zr(IV), OR = alkoxo ligand, L = ?-diketones, carboxylates) has been carried out. The volatile properties of these compounds as well as their low reactivity towards water caused that above mentioned complexes are used as TiO2 and ZrO2 precursors in CVD processes and therefore a special attention has been paid to this problem. Substitution of alkoxo groups by ?-diketonate ligands in the alkoxide/?-diketonate molar ratio of 1:1 makes possible the synthesis of monomeric complexes of the general formula [Ti(OR) 2 (?-diketonate) 2]. The use of an excess of ?-diketonate (1:2) leads to the formation of dimeric complexes ([Ti(OR)3(?-diketonate)] 2 (Fig. 2) [27]. Sensitivity of these compounds to moisture was significant lower than the parent Ti(IV) alkoxides. Suitable volatility of the mentioned complexes and thermal decomposition to TiO2 caused that their use as CVD precursors is possible. Deposition experiments proved that pure TiO2 layers of anatase form were obtained at temperatures higher than 573 K using [Ti(dpm) 2 (OiPr)v] [25] and [Ti(mpd)(mdop)(m-OMe)] 2 [93] as precursors. From Zr(IV) ?-diketonate derivatives, only [Zr(OR) 2 (thd) 2] (R = OiPr, tBu) and [Zr(OiPr)3(thd)] 2 were used for the deposition of ZrO2 by CVD methods [98]. According to the literature reports, above mentioned ?-diketonates were less reactive and easier to handle than parent alkoxides, but their volatility was significantly lower. ZrO2 layers were also prepared using [Zr(acac) 2 (hfip) 2] but in deposited films, traces of fluorine contaminations were observed [103]. Oxo-alkoxo carboxylate Ti(IV) derivatives were synthesized in reactions of Ti(IV) alkoxides with carboxylic acids (Fig. 4). The structure of these complexes consists of oxo-metallic skeletons (Fig. 5), which size and structure depends on (a) metal alkoxide/carboxylic acid molar ratio, (b) type of alkoxide and carboxylate ligand, and (c) reaction temperature. Results of these works suggest that Ti(IV) complexes, which structure consists of [Ti6O6(OR4)6(OOCR')6] (R = OiPr, nBu, iBu, R' = H, Me, tBu, CH2tBu, C(CH3)2Et, C6H4Oph) clusters are the most stable (Fig. 7) [34, 44]. These types of Ti(IV) complexes were also prepared in the reaction of Ti(IV) trimethylsiloxide with 2 fold exces of organic acids [45]. Thermolysis of [Ti6O6(OR4)6(OOCR')6] proceeds with their partialy decomposition and formation of a volatile and stable Ti(IV) alkoxide and Ti(IV) carboxylate [43]. Results of CVD experiments confirm that these types of complexes have promising properties as titanium dioxide precursors [88, 94]. Thin titanium dioxide films have been deposited in the temperature range 673-873 K on Si(111) substrates. The structure and surface morphology of the layers change with an increase of temperature from the large grain of TiO2 anatase (TD = 713-733 K), to close-packed crystals of rutile form (TD = 853-873 K). A result of the reaction of Zr(IV) alkoxides with organic acids are oxo/hydroxo Zr(IV) carboxylate or oxo/hydroxo Zr(IV) carboxylate alkoxides (Fig. 9) [57-59]. Their low volatility and high thermal stability makes them unsuitable for CVD processes. Application of fluorinated carboxylate ligands increases the volatility of these compounds. ZrO2 layers have been deposited by CVD using ([Zr6O4(OH)4(OiPr)6(OOCR')6] (R' = C2F5, C3F7) as precursors, at ~853 K. Analysis of the literature data showed that carboxylate substituted oxozirconium complexes can be applied for the preparation of inorganic-organic hybrid polymers [104, 105].

Słowa kluczowe

PL

kompleksy tytanu(IV); kompleksy cyrkomu(IV); struktura krystaliczna; NMR; IR; właściwości termiczne

EN

titanium(IV) and zirconium(IV) complexes; crystal structure; NMR; IR spectroscopy; thermal properties

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Wiadomości Chemiczne
• Rocznik: 2008
• Tom: [Z] 62, 3-4
• Strony: 209--236
• Opis fizyczny: bibliogr. 113 poz., tab., wykr.

Twórcy

autor

Piszczek P.

• Wydział Chemii, Uniwersytet Mikołaja Kopernika, ul. Gagarina 7, 87-100 Toruń

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