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The Inclusion of Organometallic Derivatives of Cyclotriphosphazenes Inside SiO2 Matrix and Their Conversion to Nanostructured Metal-Oxides and Phosphates
Organometallic derivatives of the cyclotriphosphazene N 3 P 3 [OC 6 H 4 CH 2 CN·TiClCp 2 ] 6 (1) , N 3 P 3 (O 6 H 5 ) 5 [OC 6 H 4 N·W(CO) 5 ] (2) , N 3 P 3 [OC 6 H 4 CH 2 CN·Mo(CO) 5 ] 6 (3) , [N 3 P 3 (O 6 H 5 ) 5 (OC 5 H 4 N·CpRu(PPh 3 ) 2 )][PF 6 ] (4) , [N 3 P 3 (O 2 C 12 H 8 ) 2 OC 5 H 4 N·Ag(P...
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| Published in: | Journal of inorganic and organometallic polymers and materials 2012-09, Vol.22 (5), p.1101-1112 |
|---|---|
| Main Authors: | , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
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| Summary: | Organometallic derivatives of the cyclotriphosphazene N
3
P
3
[OC
6
H
4
CH
2
CN·TiClCp
2
]
6
(1)
, N
3
P
3
(O
6
H
5
)
5
[OC
6
H
4
N·W(CO)
5
]
(2)
, N
3
P
3
[OC
6
H
4
CH
2
CN·Mo(CO)
5
]
6
(3)
, [N
3
P
3
(O
6
H
5
)
5
(OC
5
H
4
N·CpRu(PPh
3
)
2
)][PF
6
]
(4)
, [N
3
P
3
(O
2
C
12
H
8
)
2
OC
5
H
4
N·Ag(PPh
3
)][OSO
2
CF
3
]
(5)
, N
3
P
3
[OC
6
H
5
]
5
[OC
5
H
4
N·Cu][PF
6
]
(6)
and N
3
P
3
[OC
6
H
4
CH
2
CN·CuCl]
6
[PF
6
]
6
(7)
,were incorporated inside SiO
2
through the sol–gel method. The metal–organic nanocomposites of the general formula N
3
P
3
[OC
6
H
4
CH
2
CN·TiClCp
2
]
6
·
n
SiO
2
(G
1
)
, N
3
P
3
[OC
6
H
4
N·W(CO)
5
]·
n
SiO
2
(G
2
)
, N
3
P
3
[OC
6
H
4
CH
2
CN·Mo(CO)
5
]
6
·
n
SiO
2
(G
3
)
, N
3
P
3
(O
6
H
5
)
5
OC
5
H
4
N·CpRu(PPh
3
)
2
][PF
6
]·
n
SiO
2
(G
4
)
, [N
3
P
3
(O
2
C
12
H
8
)
2
OC
5
H
4
N·Ag(PPh
3
)][OSO
2
CF
3
]·
n
SiO
2
(G
5
)
, N
3
P
3
[OC
6
H
5
]
5
[OC
5
H
4
N·Cu][PF
6
]·(SiO
2
)
n
(G
6
)
, and N
3
P
3
[OC
6
H
4
CH
2
CN·CuCl]
6
[PF
6
]
6
·(SiO
2
)
n
(G
7
)
, were characterized by IR spectroscopy;
12
C,
31
P and
29
Si MAS NMR measurements as well as UV–Visible diffuse reflectance spectra, indicating the presence of the respective organometallic derivatives of the cyclotriphosphazene incorporated into SiO
2
. Pyrolysis of these nanocomposites under air at 800 °C gives rise to nanostructured metal-oxides and metal phosphates incorporated into amorphous SiO
2
, with the presence in some cases of complexes phase mixtures. From some precursors, we obtained metal-oxides/phosphates nanoparticles separated from the SiO
2
nanoparticles instead the oxides/phosphates nanoparticles inside the SiO
2
matrix. Additionally and for comparison purposes, we used the compound N
3
P
3
[NH(CH
2
)
3
Si(OEt)
3
]
6
as gelator. Nanocomposites
(G′
1
)
,
(G′
2
)
and
(G′
3
)
exhibited mainly morphological differences while in some cases composition differences when using TEOS as gelator. Some simple metal-containing compounds as (O
3
SCF
3
)Ag(PPh
3
)(HOC
5
H
4
N), [CuCl
2
·NC
5
H
4
OH] and [CuCl
2
·NCCH
2
C
6
H
4
OH]—which are useful models of the most complexes
(G
5
)
,
(G
6
)
and
(G
7
) 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 [(O
3
SCF
3
)Ag(PPh
3
)(HOC
5
H
4
N)][SiO
2
]
n
affords the firstly-reported materials containing Ag
2
O along with SiO
2
nanoparticles. |
|---|---|
| ISSN: | 1574-1443 1574-1451 |
| DOI: | 10.1007/s10904-012-9692-x |