J Inorg Organomet Polym (2012) 22:11011112 DOI 10.

1007/s10904-012-9692-x

The Inclusion of Organometallic Derivatives of Cyclotriphosphazenes Inside SiO2 Matrix and Their Conversion to Nanostructured Metal-Oxides and Phosphates
az Mar a Luisa Valenzuela Carlos D Riquelme Renato D az Daniel Carrillo Jose

Received: 16 March 2012 / Accepted: 2 May 2012 / Published online: 23 May 2012 Springer Science+Business Media, LLC 2012

Abstract Organometallic derivatives of the cyclotriphosphazene N3P3[OC6H4CH2CNTiClCp2]6 (1), N3P3 (O6H5)5[OC6H4NW(CO)5] (2), N3P3[OC6H4CH2CNMo (CO)5]6 (3), [N3P3(O6H5)5(OC5H4NCpRu(PPh3)2)][PF6] (4), [N3P3(O2C12H8)2OC5H4NAg(PPh3)][OSO2CF3] (5), N3P3[OC6H5]5 [OC5H4NCu][PF6] (6) and N3P3[OC6H4 CH2CNCuCl]6[PF6]6 (7),were incorporated inside SiO2 through the solgel method. The metalorganic nanocomposites of the general formula N3P3[OC6H4CH2CNTiClCp2]6nSiO2 (G1), N3P3[OC6H4NW(CO)5]nSiO2 (G2), N3P3[OC6H4CH2CNMo(CO)5]6nSiO2 (G3), N3P3(O6H5)5 OC5H4NCpRu(PPh3)2][PF6]nSiO2 (G4), [N3P3(O2C12H8)2 OC5H4NAg(PPh3)][OSO2CF3]nSiO2 (G5), N3P3[OC6H5]5 [OC5H4NCu][PF6](SiO2)n (G6), and N3P3[OC6H4CH2CN CuCl]6[PF6]6(SiO2)n (G7), were characterized by IR spectroscopy; 12C, 31 P and 29Si MAS NMR measurements as well as UVVisible diffuse reectance spectra, indicating the presence of the respective organometallic derivatives of the cyclotriphosphazene incorporated into SiO2. Pyrolysis of these nanocomposites under air at 800 C gives rise to nanostructured metal-oxides and metal phosphates incorporated into amorphous SiO2, with the presence in some cases of complexes phase mixtures. From some precursors, we
Electronic supplementary material The online version of this article (doi:10.1007/s10904-012-9692-x) contains supplementary material, which is available to authorized users.
az D. Carrillo J. Riquelme R. D az C. D mica, Facultad de Ciencias, Universidad de Departamento de Qu un oa, Casilla 653, Santiago, Chile Chile, Las Palmeras 3425 N M. L. Valenzuela (&) Departamento de Ciencias Quimica, Facultad de Ciencias Exactas, Universidad Andres Bello, Av. Republica 275, Santiago, Chile e-mail: mlvalenzuela@unab.cl

obtained metal-oxides/phosphates nanoparticles separated from the SiO2 nanoparticles instead the oxides/phosphates nanoparticles inside the SiO2 matrix. Additionally and for comparison purposes, we used the compound N3P3[NH (CH2)3Si(OEt)3]6 as gelator. Nanocomposites (G0 1), (G0 2) and (G0 3) exhibited mainly morphological differences while in some cases composition differences when using TEOS as gelator. Some simple metal-containing compounds as (O3 SCF3)Ag(PPh3)(HOC5H4N), [CuCl2NC5H4OH] and [CuCl2 NCCH2C6H4OH]which are useful models of the most complexes (G5), (G6) and (G7) were also prepared and incorporated in amorphous silica. Their pyrolytic products were compared with those of more complex cyclotriphosphazene analogous. Interestingly, the pyrolysis of the nanocomposite [(O3SCF3)Ag(PPh3)(HOC5H4N)][SiO2]n affords the rstly-reported materials containing Ag2O along with SiO2 nanoparticles. Keywords Solgel Metallic nanostructures Cyclotriphospahzenes

1 Introduction The incorporation of metal and metal-oxides nanoparticles inside a solid matrix is of considerable interesting both from a basic as well as application point of view [13]. Solid thin lms can have potential applications for electronic, containing metal nanoparticles, glass, chemical sensing/detectors, catalysis, semiconductors and computer industries [1]. Specically, the incorporation of Au nanoparticles inside solid matrices such as silica is crucial in order to yield the best catalytic activity. Therefore the methods to incorporate metal and metal-oxides nanoparticles inside a solid matrix face constant challenge [4].

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Approaches to incorporate nanoparticles inside solid matrices typically require solid-state methods. Contrarily to the solution methods aimed to obtain nanostructured materials, reported solid-state approaches to nanosized materials are scarce [5]. Among reported solid matrices SiO2 in both hexagonal ordered [6, 7] as well as amorphous [811] is the most widely studied. The typical method to incorporate metallic nanostructures inside SiO2 involves the hydrolysis of tetraethyl orthosilicate (TEOS) in presence of metal salts (usually metal nitrate). Metal oxide/SiO2 such as Fe2O3/ SiO2 [12, 13] Cr2O3/SiO2 [14] and metal/SiO2 such as Au/ SiO2, Ag/SiO2, Cu/SiO2, Pt/SiO2 and Pd/SiO2 [15, 16] have been prepared though this way for instance. Another similar approach relies on the use uses of TEOS with metal salts in presence of citric acid for the reduction. Ni, Co, Ag, Fe/SiO2 composites were obtained [17]. Hydrolysis of the metal/alkoxy as Cr(OtBu)4 in presence of HOSi(OtBu)3 affords nanostructured chromium oxides inside amorphous silica [18]. Impregnation of Cu(NO3)2 salts in a SiO2 xerogel gives CuxO [19].A different approach to yield metal oxide/SiO2, require using the precursor of the type MXnH2N(CH2)3Si(OEt)3 involving co-condensation with TEOS to give MOnSiO2 nanocomposites [20]. As an alternative method Xia et al. [21] reported a novel procedure to obtain nanocables of Ag covered with amorphous silica. The preformed Ag nanoc ber procedure. ables were covered with silica using the Sto Only two approaches aimed to incorporated organometallic compounds inside amorphous silica have been reported to date [22, 23]. One is based on the use of the precursor [22]: MLnR2P(CH2)2Si(OEt)3, MLn = Fe(CO)5, RuCl2(g6-cymene), Co2(CO)9, followed by hydrolysis in presence of Si(OCH3)4. The other approach uses the precursor cis-Ru(Cl((CO)2P(R)(R0 )(CH2)xSi(OCH3)3 in presence of TEOS [23]. Solgel processes involving phosphazenes include one where the polyphosphazenes are embedded in the silica matrix, with no linkages between the

phosphazene and the silica matrix [24], and another in which the phosphazene units are covalently linked to the matrix by hydrolysis of the precursor N3P3(CH2Si(OMe)3)6 [25].More recently, hybrid organicinorganic materials from gelation of N3P3Cl6 using several gelation reagents, were prepared [26]. Solgel processes using the cyclic precursor with the sililated groups linked to the polyphosphazenes polymeric chains have also been recently studied [27]. We previously reported the synthesis of organocyclophosphazene-silica composites which constitute new materials able to retain metal complexes at trace levels [28]. Theoretical studies of the surface functionalization of silica with N3P3Cl6 have also been reported [29]. However, to best of our knowledge no organometallic derivatives of cyclotriphosphazene included inside silica have been reported. In this work we describe the inclusion of a series of organometallic derivatives of cyclotriphosphazene inside amorphous silica and their use as precursors of metallic nanostructured materials incorporated inside silica. This new approach to metallic nanostructured materials inside amorphous silica involves two-step synthesis: inclusion of the respective organometallic derivative of cyclotriphosphazene and their pyrolysis at 800 under air see, Scheme 1. In the rst step the organometallic derivative of cyclotriphosphazene is incorporated inside silica to give xerogel materials of the general formula MLn(SiO2)n (MLn = organometallic derivative of cyclotriphosphazene). To our knowledge these are the rstly described compounds having an organometallic derivative of cyclotriphosphazene incorporated inside silica matrix. Subsequent pyrolysis of these xerogels at 800 C affords metallic nanostructures included inside silica. These metallic products of the general formula MxOy/MxPyOz(SiO2)n are similar to those of the pyrolytic product using the organometallic derivative of cyclotriphosphazene without silica as precursor. We have previously reported a solid-state method to prepare metallic, metal oxide and metal phosphates starting from the solid-

Scheme 1 General strategy of the new approach to afford metallic nanostructured materials

N3P3(OC6H5)6-n (O-C6H4-X MLn)n

TEOS [N3P3(OC6H5)6-n (O-C6H4-X MLn)n] [SiO2]n Pyrolysis

HOC6H4X = HOC5H4N X = CH2CN MLn = Cp2TiCl, W(CO)5, Mo(CO)5, CpRu(PPh3)2, Ag(PPh3), SO3CF3, CuCl

Air, 800C

M/MxOy/M(PxOy)z

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J Inorg Organomet Polym (2012) 22:11011112 Table 1 Preparative detail of the gels Gelant agent Organometallic N3P3[OC6H4CH2CNTiClCp2]6 [PF6]6 N3P3(O6H5)5 [OC6H4NW(CO)5] N3P3[OC6H4CH2CNMo(CO)5]6 [N3P3(OC6H5)5(OC5H4NCpRu(PPh3)2)][PF6] [N3P3(O2C12H8)2OC5H4NAg(PPh3)][OSO2CF3] N3P3[OC6H5]5 [OC5H4NCu] [PF6] N3P3[OC6H4CH2CNCuCl]6[PF6]6
a b c d

1103

Si(OC2H5)4 g complex 0.10c

b b

N3P3{NH [CH2]3Si[OEt]3}6 g Gelant 1.59c

b b

g H2O 0.55c
b b

g complex 0.20c 0.10

b b b b c

g Gelant 0.068c 2.58

b b b b c

g H2Oa 0.063c 3.18c 19.22d

b b

0.25d

1.55d

0.21 0.175 0.342 0.142

0.142 0.811 2.122 0.821

0.5 0.276 0.726 0.276

H2O nanopure No gelation was obtained 1:3 ratio organometallic/TEOS. Other ratio 1:5 and 1:10 were also performed 1:10 ratio

Fig. 1 29Si MAS NMR (a), 31P MAS NMR (b) and 12C MAS NMR (c) of the gel (G0 1). For 31 P MAS NMR also a heptuplet at -144.34 ppm (not shown) was observed

sate pyrolysis of organometallic derivatives of cyclotriphosphazene [3033]. Then using this approach with the precursors MLn(SiO2)n metallic products, metallic oxides or

metallic phosphates are expected as products included inside amorphous silica and/or separate metallic, metal-oxides or metallic phosphates and SiO2 nanoparticles.

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2 Experimental 2.1 Preparation of the organometallic precursors [N3P3[OC6H4CH2CNTiClCp2]6][PF6]6 [30], N3P3(O6H5)5 [OC6H4NW(CO)5] [30], N3P3[OC6H4CH2CNMo(CO)5]6 [33], [N3P3(O2C12H8)2OC5H4NAg(PPh3)][OSO2CF3] [31], [N3P3[OC6H5]5 [OC5H4NCu][PF6] [35] and [N3P3[OC6H4 CH2CNCuCl]6][PF6]6 [35] were prepared as previously reported. 2.2 Preparation of [N3P3(OC6H5)5(OC5H4NCpRu(PPh3)2)][PF6] N3P3(O6H5)5(OC5H4N) 0.238 g (1.52 9 10-4 mmol) and CpRu(PPh3)2Cl 0.249 g (3.42 9 10-4 mmol) in a Schlenk tube using methanol (50 ml) and in presence of NH4PF6 0.084 g (5.15 9 10-4 mmol) were stirred at room temperature for 24 h. The solution was then concentrated to ca. 10 ml and a mixture of n-hexane-diethylether was added. The supernatant was removed by decantation and the yellow solid was dried under vacuum. Yield 63 %. IR (KBr pellet, cm-1) 3054w, 2963w, 1701m, 1488s, 1434m, 1269m, 1196m, 1177vs, 1161w, 1089w, 1024m, 950vs, 834m, 824m, 772m, 691m, 533m, 520m, 499m. 1H-NMR (CDCl3, ppm) 8.69 (o-H,OC5H4N); 6.38 (m-HOC5H4N); 7.7, 7.67.0, 7.53, 6.94 P(C6H5)3; 7.07.5 (OC6H5). 31P NMR {H} (CDCl3, ppm) 25.30 P(C6H5)3, 8.76 (N3P3 ring) -144.12 (PF6). Anal. Calcd. for C76H64N4O6F6P7Ru: C 58.45, H 4.10, N 3.5; found C 61.94, H 3.46, N 3.72.
Table 2 Summary of the pyrolytic products from gel precursors as determined from XRD Gel G1
0

2.3 Gelations 2.3.1 Using TEOS: General Procedure The organometallic/metallic derivative of cyclotriphosphazene (see Table 1 for details) was dissolved in 50 ml of ethanol and then Si(OEt)4 (0.81.6 g) followed by 0.20.8 g of nanopure water and NH4F 0.0197 g as catalyst. The beaker was covered with paralm and the reaction mixture was left at room temperature until dryness. Further details for all the organometallic are shown in Table 1. 2.3.2 Using N3P3{NH[CH2]3Si[OEt]3 To the respective organometallic (see details in Table 1) dissolved in ethanol, N3P3{NH[CH2]3Si[OEt]3}6 was added in a beaker, followed by water and NH4F according to amounts given in Table 1. The mixture was stirred until dryness after which photographs of the gels were taken. 2.4 Pyrolysis The pyrolysis experiments were carried out, as previously reported [3033], by pouring a weighed portion (0.050.15 g) of the gel on aluminum oxide boats placed in a box furnace, heated from 25 to 300 C and then to 800 C, and annealed for 2 h.

Table 3 Summary of the morphologies of pyrolytic products from gel precursors as determined from SEM
Gel Ratio metala/ gelator 1:3 1:5 1:10 G0 2 1:3 1:10 G0 3 G1 1:5 1:10 1:3 1:5 1:10 G4 G5 G6 G7 1:5 1:10 1:10 1:5 1:5 Products Morphology

Ratio metala/gelator 1:3 1:5 1:10

Products SiO2; TiP2O7; TiO2 SiP2O7; SiO2; TiP2O7; Ti9O17 SiP2O7; P4O7; SiO2; Ti7O13 SiP2O7/SiO2/P2O5; W18O49 WP2O7; SiO2 MoP2O8/MoO3/P2O5; SiO2 MoO3/SiO2/MoP2O7 Ti5O9; Ti(PO3)3; SiP2O7 SiP2O7; Ti4O7; Ti3O5; Ti2O3; P4O9 Ti(PO3)3; TiP2O7; TiO2; SiP2O7 Ru(P3SiO11); SiO2 Ru(P3SiO11); SiO2 Ag4(P2O7); SiO2 CuO; Si3(PO4)3SiO22 P2O5 CuO; Cu2P2O7; Cu3(PO4)2

G0 1

SiO2, TiP2O7, TiO2 SiP2O7; SiO2; TiP2O7; Ti9O17 SiP2O7; P4O7; SiO2; Ti7O13 SiP2O7/SiO2/P2O5; W18O49 WP2O7; SiO2 MoP2O8/MoO3/P2O5; SiO2 MoO3/SiO2/MoP2O7 Ti5O9; Ti(PO3)3; SiP2O7 SiP2O7; Ti4O7;Ti3O5;Ti2O3; P4O9 Ti(PO3)3; TiP2O7; TiO2; SiP2O7 Ru(P3SiO11); SiO2 Ru(P3SiO11); SiO2 Ag4(P2O7); SiO2 CuO; Si3(PO4)3SiO22 P2O5 CuO; Cu2P2O7; Cu3(PO4)2

Fibrous 3-D network 3-D network of fused grains Foam 3D octopus-branch-, shbone-like Two zones: foamy and dense Separated grains Fused grains Dense Dense Foams, dense Dense Porous Foams Foams

G0 2 G3 G1
0

1:3 1:10 1:5 1:10 1:3 1:5 1:10

G4 G5 G6 G7
a b

1:5 1:10 1:10b 1:5b 1:5b

Metal as the organometallic derivative of cyclotriphosphazene No gelation was obtained with other ratio M/Si

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J Inorg Organomet Polym (2012) 22:11011112 Fig. 2 XRD of (G1) (left) and their t with standard patterns
Compound 2 (pattern) 11.25 Ti5O9 16.93 21.94 26.39 28.96 16.05
2 10 20 30 40 50 60

1105
2 (sample) 11.21 16.52 21.99 26.28 28.94 16.09 18.40 23.31 24.69 25.79 13.69 18.40 24.06 24.37 27.71

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

Lin (Cps)

Ti5O9

Ti(PO3)3

18.74 23.87 24.87 25.64 13.70 18.76

2-Theta - Scale

SiP2O7

23.91 24.39 27.61

2.5 Characterization Infra-red (IR) spectra were recorded on an FT-IR PerkinElmer Spectrum BX II spectrophotometer. X-ray diffraction (XRD) was performed at room temperature on a Siemens D-5000 diffractometer with h2h geometry. The XRD data was collected using CuKa radiation (40 kV and 30 mA). Scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) were acquired with a JEOL 5410 SEM with a NORAN Instrument micro-probe transmission microscope. TEM images were recorded on a JEOL SX 100 transmission microscope, using ne powdered samples dispersed in water and dropped on a conventional carbon-wasted copper grid.

3 Results and Discussion 3.1 Formation of the (Gi), and (G0 i) Xerogels The organometallic/metallic derivatives of cyclotriphosphazene utilized in this work have been synthesized as previously reported [30, 34, 35].The inclusion of the organometallic derivatives inside silica involves the hydrolysis of TEOS in presence of the cyclic phosphazene. According to the solgel method, hydrolysis of TEOS using a weakly acidic catalyst as NH4PF6 in ethanol/water

mixtures affords amorphous silica. Gelation occurs within the day/min to give white or yellow gels depending on the color of the organometallic compounds. The presence of the organometallic derivative of cyclotriphosphazene inside SiO2 was corroborated by IR as well as solid-state 12C, 31 P and 29Si, MAS NMR measurements. For instance, for the compound (G0 1), the 29Si MAS NMR spectroscopy conrms the presence of mainly T3 (-65.47 ppm) structures corresponding to RSi(OSi)3 links in the gels typical of condensation of TEOS [9] (see Fig. 1). A minor amount of T2 (-57.10 ppm) and some traces of T1 (-49.53 ppm) corresponding to a Si(OSi)2OH and RSi(OSi)(OH)2 links typically of only partially hydrolyzed TEOS are also observed (see Fig. 1a). A signal at 13.32 ppm in their 31P MAS NMR, typical of the N3P3 [25] demonstrate the presence the phosphazene ring in the silica matrix (see Fig. 1b). Additionally, the 12C MAS NMR spectrum exhibits signals at 133.54 ppm (OC5H4C), 119.85 ppm (CN), 25.71 ppm (CH2) typical of the cyclotriphosphazene ring (see Fig. 1c). On the other hand two signals at 55.57 and 44.57 ppm indicate the presence of incompletely hydrolyzed fragments from TEOS. The other xerogels compounds exhibit similar signals pointing to the formation of similar silica matrix with the included corresponding phosphazene. Some others selected spectra are shown in supporting information S1.

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1106 Fig. 3 XRD of pyrolytic products from gel (G6) (a) and (G7) (b), SEM images from (G6) (c) and (G7) (d) and TEM images from (G6) (e) and (G7) (f) i.e. (G6) and (G7) as shown in Fig. 3c, d. Although two morphology are mainly foamlike, ne details between them both are different

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Additional evidence for the inclusion of the respective organometallic derivative of cyclotriphosphazene inside silica arises from their UVVisible diffuse reectance

spectra. For instance for (G1), the spectrum exhibits two maxima at 413 and 450 nm that are typical absorptions of N3P3[OC6H4CH2CNTiClCp2]6 with maxima at 391 and

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J Inorg Organomet Polym (2012) 22:11011112 Fig. 4 SEM images (a) and (b), and EDAX for the G4 for the 1:5 (c) and 1:10 (d) ratio Ru/ TEOS

1107

419 nm, see supporting information S2, while in this region the SiO2 matrix, does not absorb. For (G0 1) a similar absorption pattern was observed. It is interesting to note that for equivalent concentrations, the absorptions of the Cp2TiCl chromophore follow the intensities in the expected order corresponding to the 1:3, 1:5, 1:10 molar ratio i.e. Int (1:3) [ Int (1:5) [ Int (1:10), see supporting information S2.For (G0 2) the typical absorption of the W(CO)5 chromophore was also observed (see supporting information S2). IR spectroscopy also provides some insights about the xerogels. In all the spectra the typical m(P=N) bands appear in the range 1,2691,100 cm-1 [34, 35]. Among known classications of hybrid organo-inorganic nanocomposites [810] the (Gi) solid can be classied as class I organoinorganic hybrid, characterized by absence of covalent or ionic covalent bonds between the organic and inorganic compounds. 3.2 Pyrolysis of the (Gi), and (G0 i) Xerogels Pyrolysis of the (Gi), and (G0 i) xerogels under air and at 800 C indicate the formation of mainly nanostructures

metal-oxides and metal phosphates included in silica or separated SiO2 nanoparticles. Complex phase mixtures were also found in some cases. Composition of the products was determined by XRDs of the powder; however, a broad diffraction peak around 2h = 20, normally found in metallic derivatives incorporated in silica [822], interfered with the observation of characteristic peaks of the metal-oxides and metal phosphates included in silica. A detailed analysis of the XRD patterns of some selected gels is shown in supporting information S3. A summary of the main pyrolytic products determined by powder XRD is shown in Table 2. For the pyrolytic products from (G1) a broad peak was observed in the range 2h = 1530 (see Fig. 2). This diffraction patterns is typical of some (TiO2)(SiO2)n nanocomposites [3638]. It is interesting to note the complex mixture of several titanium oxides from pyrolysis of gel (G1) especially from the mixture 1:5, compared with the products from the analogue (G0 1). However, the methods to obtain titanium oxides usually afford complex mixtures [39, 40]. In addition a marked dependence of the composition of the pyrolytic products with the ratio metal/ gelator is also observed from Table 2. For instance, when

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1108 Fig. 5 SEM images for three zones (a) and (b) and (c) and EDAX (d) for the pyrolytic product from (G0 2)

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comparing the pyrolytic products from the ratios 1:3, 1:5, 1:10 for the gel (G1), titanium oxides with different composition were obtained. Interestingly we observed the presence, in some cases, of solgel glasses [4145]. Although the glasses containing the phase SiO2/P2O5 are common [43], the glasses MoP2O8/MoO3/P2O5 and MoO3/SiO2/Mo2P2O7 are less common. Parkin found phases MoO3/Mo2P2O7 from polyoxomolybdates [41] but no information about the nanostructured glasses neither data related to formation of glass Si3(PO4)3/SiO2/P2O5 was reported. Also interesting is the occurrence of SiP2O7 in almost all the products. This material is normally obtained by reaction of SiO2 with P2O5 [4245] so that the most likely way can be from reaction of SiO2, obtained from the solgel process, with P2O5 formed by oxidation of the PN ring of phosphazene. In the case of the (G6) and (G7) the pyrolytic products exhibit XRD patterns similar to those reported for nanocomposites of the type [CuO][SiO2]n [4648] (see Fig. 3a, b) but most complexes were due to the presence of other phases. Interestingly, the pyrolysis of the precursors/

models [CuCl2NC5H4OH]nSiO2 and [CuCl2NCCH2C6H4OH]nSiO2 affords pure CuO together with nanoparticles of SiO2 (supporting information S4). Therefore, it is clear that the presence of several phases arise from the phosphorus in the PN ring forming metallic phosphates and pyrophosphates derivatives. Despite some methods to prepare Ag nanoparticles inside SiO2 are available [21, 4951] no Ag2O nanoparticles inside SiO2 have been reported. Ag2O itself, is an interesting material due to its multiple applications as preservatives, colorants, and for electrode materials [51]. It is a semiconductor with a band gap of 2.25 eV and their thin lm of nanoscale of Ag2O particles has been found to show an interesting photoactivated intermittent uorescence behavior which has potential applications in rewritable optical recording media [52].Nonetheless only few methods to prepare Ag2O nanoparticles have been reported [5155]. The pyrolytic products from [O3SCF3)Ag(PPh3) (HOC5H4N)][SiO2]n afford the rstly described materials containing Ag2O joined to SiO2 nanoparticles. Their XRD exhibitas shown in supplementary materials S5the presence of Ag2O nanoparticles and SiO2 as crystobalite.

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J Inorg Organomet Polym (2012) 22:11011112 Fig. 6 SEM images for two zones (a and b) and EDAX (c) for the pyrolytic product from (G0 1)

1109

In addition, 29Si MAS NMR spectroscopy provides structural information about the silica matrix. All the pyrolytic products exhibit peaks around 110 ppm typical of Si(OSi)4 moieties in the (SiO2)n matrix [9]. A less intense peak around 100 ppm also suggests the presence of minor amount of EtOSi(OSi)3 fragments within the structure of the silica matrix see supporting information S6. As expected, no signicant signals of organic matter were observed as evidenced by the absence or weakly 31P MAS NMR and 12C MAS NMR signal in their respective spectra. IR spectroscopy also affords structural information about the silica matrix. Spectra of the pyrolyzed gels exhibits a very simple pattern with an intense band around 1,100 cm-1 and a less intense one at 800 cm-1 which can be assigned to SiO and SiO-Si vibrations respectively, of the silica [5658]. A medium-intensity band around 470 cm-1 is assigned to a SiOSi rocking modes. Also, the band around 1,100 cm-1 appears broader due to the presence of P=O bands arising from metal pyrophosphates and phosphates [59]. Additionally, a weak band around 1,640 cm-1 was assigned to an overtone of the OH stretching band, of the residual SiOH bonds [5658]. This

latter appears in the range of 4,3203,420 cm-1. Representative IR spectrums are shown in supporting information S7. The morphology of the pyrolytic products was investigated by SEM. Dense-to- porous morphologies were found. Instance, foam-like morphology was observed for the pyrolytic product from the gel (G6) and (G7) as shown in Fig. 3c, d. It was also observed that the morphology is dependent on the nature of the precursor for both gels precursors containing copper linked to different spacer of the phosphazene ring A (4)/TEOS dependent morphology, on the ratio, was found for the pyrolytic product from (G4): for the 1:5 ratio a foam-like morphology was obtained while for the 1:10 ratio a denser morphology was observed (see Fig. 4a, b). The EDAX analysis shows the presence of ruthenium, Si, oxygen and phosphorus with the correct relation Ru to Si according the 1:5 and 1: 10 gelation ratio (see Fig. 4c, d). Interesting and unusual morphologies were found for (G0 2) gel in 1:3 gelation ratios. Three zones with different morphologies were observed: one shbone-like nanostructure, another one with a 3D octopus-branch-like and

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1110 Fig. 7 TEM images of some pyrolyzed products from gels precursors : a, b from (G1) with ratios 1:10 and 1: 5 respectively, c from (G4), d, e from (G0 4) and f from (G0 3)

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another with 3-D foam (see Fig. 5ac). EDAX analysis shows evidence of Si, P, W and O in agreement with the phases found for the product. Similar shbone-like shapes have been observed for MgO nanostructure [60] and ZnS nanowires [61]. Morphology of pyrolytic product from gel (G0 1) exhibits a 3-D network of fused grains as shown in Fig. 6a, b. The EDAX evidences the normal presence of Ti, Si,P and O (see Fig. 6c). Morphologies for other pyrolysis gels products are normal and are summarized in Table 3.

TEM images give some details of the size and shapes of the nanostructured products- when proceed as shown in Fig. 7. For (G1) with ratios 1:10 and 1:5, agglomerates of joined nanoparticles were observed (see Fig. 7a, b) respectively. The shape can be viewed as nanoparticles of about 20 nm for the 1:10 ratio product and more diverse sizes for 1:5 ratios in the range from 20 nm to larger agglomerates. Thus these are typical TEM images for nanostructured products obtained from solgel processing [62, 63]. Similar TEM images for other metalsilica nanocomposites have been observed [11, 12, 15, 20].

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1111

For (G4) two shapes were also observed: one small, nearly round of about 20 nm and another with more agglomerated structures (see Fig. 7c). Also, similar TEM images, with two zones different, have been observed for TiO2SiO2 nanocomposites [64]. On the other hand, tree branches of SiO2 decorated with titanium oxides were observed for (G0 1) (see Fig. 7d, e). Although several nanostructures with varied shapes have been described, few tree-like branches shapes have been reported [6466]. The nanotubes/nanorods have close 660 nm width with several micrometers in longitude. Attempts to clarify if these shapes are nanotubes and/or nanorods using HRTEM methods were unsuccessfully due to the high energy of the e-beam on the TEM microscopy that destroys the sample. Similar shapes for GaP nanotree have been described [64] and for AlN, a model of the growth mechanism of tree-like shapes has been proposed [65]. Other similar reports shows similar TEM images not named as tree-like branched shapes, i.e. nanotubes with similar arrangements to those shown in Fig. 7d, e: Cu2-xSe nanotubes [66] and CdS prepared by a solvothermal method [67]. In addition, Bi2Se3 prepared by thermal reaction of BiCl3 and Se exhibiting similar TEM image has been reported [68]. On the other hand, the TEM images of the products from the thermal decomposition of the molecular precursor Cd(diethyldithiocarbamate)2, nanorods of CdIn2S4, are similar to those of Fig. 7d, e [69]. For (G0 3), urchins-like tree branches joined by nanotubes were observed (see Fig. 7f, g). Although several nanourchins-like structures have been described [70, 71] no single micro-urchins joined by nanotubes like those reported here, have been described. The observed urchins are larger in the range from 200 nm to 1 lm. Finally, for the pyrolytic product from precursors (G6) and (G7), agglomerates were observed as is shown in Fig. 3e, f.

Pyrolysis under air and at 800 C of these nanocomposites gives rise to nanostructured metallic oxides and/or phosphates and in some cases using Ag precursors, metallic Ag. The high temperatures and the silica environment induce the formation of Ag2O (instead Ag) together with SiO2 nanoparticles, providing the rst example of incorporation of this interesting semiconductor into a solid matrix of SiO2 nanoparticles.
Acknowledgments Financial support from Fondecyt (Project 1085011) is gratefully acknowledged.

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4 Conclusions Organometallic derivatives of cyclotriphosphazenes have been incorporated inside amorphous silica using the sol gel method. Spectroscopic data indicate that the hybrid organicinorganic materials can be classied as class I according to the classications given by Sanchez [72,] i.e. absence of covalent or ionic-covalent bonds between the cyclic phosphazene and the inorganic component (amorphous silica); only Van der Waals hydrogen bonding or electrostatic forces are present. This is, to the best of our knowledge, the rst example of inclusion of organometallic derivatives of cyclotriphosphazenes inside silica amorphous.

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