Transformation of molecular compounds with Ba(Sr)/Al/Si and Ca(Sr, Ba)/Ti(Zr, Hf)/Si heteroelements as new efficient route to metal silicate materials†
Abstract
Silicon-based moieties were anchored in heterometallic alkoxide platforms to obtain molecular clusters based on the M–O–M′–O–Si motif for the generation of mixed-metal silicate materials. Single-source molecular precursors with structures [M{(μ-ddbfo)2Al(OSiPh3)2}2], where dbbfoH = 2,3-dihydro-2,2-dimethylbenzofuran-7-ol and M = Ba (1), Sr (2), [Sr4Ti2(μ6-O)(μ3,η2-OCH2CH2OMe)8(η-OCH2CH2OMe)2(OSiPh3)4] (3), [Sr4M′2(μ4-OH)(μ3,η2-OCH2CH2OMe)4(μ,η2-OCH2CH2OMe)6(μ-X)(OSiPh3)4] (4, with M′ = Zr and X = Cl; 5 with M′ = Hf and X = OH), [Sr3Hf2(μ5-O)(μ3,η2-OCH2CH2OMe)4(OCH2CH2OMe)4(OSiPh3)4] (6), and [Ca2M′2(μ3-OH)2(μ,η2-OCH2CH2OMe)4(η2-HOCH2CH2OMe)2(η-OCH2CH2OMe)2(OSiPh3)4] for M′ = Zr (7), Hf (8), were prepared by substitution of methyl groups, using Ph3SiOH or chloride atoms with KOSiPh3, in [M{(μ-ddbfo)2AlMe2}2] (M = Sr, Ba) or [M4M′2(μ6-O)(μ3,η2-OCH2CH2OMe)8(OCH2CH2OMe)2(HOCH2CH2OMe)xCl4] (M = Ca, Sr, Ba, M′ = Ti, Zr, Hf and x = 0, 4). The precursors were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray structural analysis. Thermal decomposition of compounds 1–8 at 1000 °C led to formation of ceramic materials that consisted of mixed-metal oxide nanocrystallites embedded in an amorphous SiO2 matrix. Compounds 1 and 2 decomposed to BaAl2Si2O8 and SrAl2Si2O8 aluminosilicates, 4 gave a mixture of SrSiO3, ZrO2, SrZrO3 and Sr7ZrSi6O21, 5 and 6 gave mixtures of various compounds, including SrHfO3, Hf0.96Si0.04O2, and SiO2, 7 lead to CaZrO3, ZrO2 and Ca3ZrSi2O9 and 8 gave a HfO2, Ca2HfSi4O12 and SiO2 phase. The thermolysis of compound 3 gave SiO2 particles of average size 40–90 nm, which contained spherical SrTiO3, SrSiO3 and Sr2TiSi2O8 nanocrystallites of diameter 5–16 nm.