COOH-Functionalized Hybrid Organic–Inorganic Material
(
1
(
50 mL) was added dropwise to a hot solution of NaCN (9.46 g,
93.0 mmol) and 18-crown-6 (0.20 g, 1.93 mmol) in acetonitrile
300 mL). The resulting mixture was heated to reflux with stirring
Synthesis of the Nickel(II) Salt of COOH-POSS (COONi-POSS):
This material was prepared according to the procedure described
for COOCu-POSS. A green solid was obtained in 96% yield. EDS
analysis (atomic): Na/Si = 0 and Ni/Si = 0.48.
for 7 d. The reaction mixture was cooled to room temperature, and
the salts were eliminated by filtration. MeCN was evaporated under
vacuum, and the sticky residue was washed with pentane
Supporting Information (see footnote on the first page of this arti-
cle): GPC profile of Cl-POSS after acid treatment. ATR FTIR
spectrum for COOH-POSS. Nitrogen adsorption–desorption iso-
therms at 77 K for COOH-POSS. Real part of the global conduc-
tivity (σac) as a function of the frequency (f) of dry COOH-POSS
(
5ϫ50 mL) to yield CN-POSS (8.90 g, 98%) as a white powder.
1
H NMR (300 MHz, [D
m, 16 H, SiCH CH
CN) ppm. Si{ H} NMR (40 MHz, [D
6
6
]acetone): δ = 0.90 (m, 16 H, SiCH
2
), 1.81
12.0 Hz, 16 H,
]acetone):
]acetone): 12.1
CN)], 120.0 (CN)
ppm. IR (KBr): ν˜ = 2941, 2884 and 2799 (νC–H), 2243 (νCN), 1152
3
(
2
2
), 2.50 (t,
HH
J =
29
1
SiCH
2
CH
2
CH
2
2
9
13
1
at different temperatures. Si CP-MAS NMR spectrum of CO-
ONa-POSS.
δ = –69.2 ppm. C{ H} NMR (75 MHz, [D
SiCH ), 20.2 [(SiCH CH ) and (SiCH CH CH
6
(
2
2
2
2
2
2
–1
and 1029 (νSi–O–Si) cm . C32
H 5.03, N 11.65, Si 23.37; found C 39.50, H 5.12, N 11.02, Si 22.82.
MALDI-TOF MS: m/z = 984.20 [M + Na] . TGA: weight loss of
4
48 8 8
H N O12Si (961.40): calcd. C 39.98,
Acknowledgments
+
The authors thank Dr Philippe Dieudonné (Laboratoire Charles
Coulomb, UMR 5221, UM2) for SAXS measurements,
Dr Philippe Gaveau (ICGM, Plateau technique UMR 5253, UM2)
for solid-state NMR measurements, Dr Sophie Monge-Darcos for
size exclusion chromatography analysis, and the University of
Montpellier for financial support.
9.9% between 25 and 700 °C.
Synthesis of Oligomeric Silsesquioxane-octapropionic Acid (COOH-
POSS): To CN-POSS (6.00 g, 6.25 mmol) was added sulfuric acid
solution (9 m, 150 mL) at room temperature. The mixture was
stirred at 25 °C for 1 h and 100 °C for 10 h. The reaction mixture
was cooled to room temperature before water (400 mL) was added.
The solid was recovered by filtration and washed with water
[
1] a) R. J. P Corriu, N. Anh, Molecular Chemistry of Sol-Gel De-
rived Nanomaterials, Wiley-Blackwell, Chichester, UK, 2009; b)
A. Cisielski, C.-A. Palma, M. Bonini, P. Samori, Adv. Mater.
(
1
3ϫ100 mL), acetone (50 mL), and ether (50 mL). After drying at
20 °C under vacuum for 12 h, COOH-POSS (6.90 g, 99%) was
13
obtained as a white powder. C NMR (75 MHz, CP-MAS): δ =
1
1
2010, 22, 3506–3520; c) K. Yoosaff, A. Llanes-Pallas, T. Mar-
3.0 (SiCH
2 2 2 2 2 2
), 19.1 (SiCH CH ), 37.0 (SiCH CH CH COOH) and
angoni, A. Belbakra, R. Marega, E. Botek, B. Champagne, D.
Bonifazi, N. Armaroli, Chem. Eur. J. 2011, 17, 3262–3273.
2] a) J. A. Barreto, W. O’Malley, M. Kubeil, B. Graham, H. Ste-
phan, L. Spiccia, Adv. Mater. 2011, 23, H18–H40; b) D. Tuncel,
H. V. Demir, Nanoscale 2010, 2, 484–494; c) Y. S. Zhao, H. Fu,
A. Peng, Y. Ma, D. Xia, J. Yao, Adv. Mater. 2008, 20, 2859–
29
80.0 (COOH) ppm. Si NMR (60 MHz, CP-MAS): δ = –68.8
1
ppm. H NMR (600 MHz, MAS): δ = 0.84, 1.81, 2.32 (3s, 6 H,
SiCH CH CH ) and 10.20 (s, 1 H, COOH) ppm. IR (ν, KBr): ν˜ =
250–2700 (νO–H of carboxylic acid), 2944 and 2800 (νC–H), 1703
[
[
2
2
2
3
–1
56 8
(νC=O), 1105 and 1008 (νSi–O–Si) cm . C32H O28Si (1113.45):
calcd. C 34.52, H 5.07, Si 20.18; found C 33.25, H 5.26, Si 20.33.
TGA: weight loss of 60.1% between 25 and 800 °C.
2876.
3] a) J.-M. Lehn, Supramolecular Chemistry, 1995, Wiley-VCH,
Weinheim, Germany; b) W. Jones, C. N. R. Rao, Supramolec-
ular Organization and Materials Design, 2002, Cambridge Uni-
versity Press; c) R. W. Saalfrank, H. Maid, A. Scheurer, Angew.
Chem. 2008, 120, 8924; Angew. Chem. Int. Ed. 2008, 47, 8794–
8824; d) P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Ter-
raneo, Angew. Chem. 2008, 120, 6206; Angew. Chem. Int. Ed.
Proton Exchange Study of COOH-POSS with D
25 mg) was added to of D O (4 mL) at room temperature under
an argon atmosphere. The resulting suspension was stirred for
2
O: COOH-POSS
(
2
3
1
0
0 min and filtered under argon. The obtained solid was dried at
1
00 °C under vacuum for 20 h. H NMR (600 MHz, MAS): δ =
2008, 47, 6114–6127; e) S. Clément, F. Meyer, J. De Winter, O.
2 2 2
.84, 1.81, 2.32 (3s, 6 H, SiCH CH CH ) and 11.10 (s, 0.5 H,
Coulembier, C. M. L. Vande Velde, M. Zeller, S. Sergeiev, J.-Y.
Balandier, R. Lazzaroni, Y. Geerts, P. Dubois, J. Org. Chem.
2010, 75, 1561–1568.
COOH) ppm.
Synthesis of the Sodium Salt of COOH-POSS (COONa-POSS): A
solution of sodium acetylacetonate (2.0 g, 16.26 mmol) in dry
EtOH (20 mL) was added at room temperature to a suspension
of COOH-POSS (2.25 g, 2.03 mmol) in dry EtOH (20 mL). The
mixture was stirred at 25 °C for 10 h. The resulting solid was col-
lected by filtration and washed twice with hot EtOH (20 mL) to
remove acetylacetone. After drying, COONa-POSS (2.57 g,
[4] A. Mehdi, C. Reye, R. J. P. Corriu, Chem. Soc. Rev. 2011, 40,
5
63–574.
[
[
5] A. Mehdi, J. Mater. Chem. 2010, 20, 9281–9286.
6] a) R. J. P. Corriu, E. Lancelle-Beltran, A. Mehdi, C. Reye, S.
Brandès, R. Guilard, Chem. Mater. 2003, 15, 3152–3160; b) F.
Lerouge, G. Cerveau, R. J. P. Corriu, New J. Chem. 2006, 30,
1364–1376.
29
2
(
=
.00 mmol, 98%) was obtained as a white powder. Si NMR
60 MHz, CP-MAS): δ = –67.7 ppm. EDS analysis (atomic): Na/Si
0.97.
[
7] C. J. Brinker, G. W. Scherrer, Sol-Gel Science, the Physics and
Chemistry of Sol-Gel Processing, 1st ed., Academic Press, San
Diego, 1990.
[
[
[
8] J. C. Zhou, M. H. Chuang, E. H. Lan, B. Dunn, B. P. L. Gill-
man, S. M. Smith, J. Mater. Chem. 2004, 14, 2311–2316.
9] E. Besson, A. Mehdi, A. Van der Lee, H. Chollet, C. Reye, R.
Guilard, R. J. P. Corriu, Chem. Eur. J. 2010, 16, 10226–10233.
10] a) D. B. Cordes, P. D. Lickiss, F. Rataboul, Chem. Rev. 2010,
110, 2081–2173; b) P. D. Lickiss, F. Rataboul, Adv. Organomet.
Chem. 2008, 57, 1–116.
Synthesis of the Copper(II) Salt of COOH-POSS (COOCu-POSS):
COONa-POSS (0.50 g, 0.39 mmol) was added to a solution of
CuCl (0.31 g, 2.33 mmol) in water (20 mL) at room temperature.
2
After 10 h of stirring at 25 °C, the solid was collected by filtration,
washed with water (4ϫ10 mL), and dried under vacuum to give
COOCu-POSS (0.50 g, 0.37 mmol, 95%) as a blue powder. EDS
analysis (atomic): Na/Si = 0 and Cu/Si = 0.48.
[11] a) V. Ervithayasuporn, J. Abe, X. Wang, T. Masushima, H.
Murata, Y. Kawakami, Tetrahedron 2010, 66, 9348–9355; b) X.
Yang, J. D. Froehlich, H. S. Chae, S. Li, A. Mochizuki, G. E.
Jabbour, Adv. Funct. Mater. 2009, 19, 2623–2629; c) M. Y. Lo,
C. Zhen, M. Lauters, G. E. Jabbour, A. Sellinger, J. Am. Chem.
Soc. 2007, 129, 5808–5809; d) J. D. Froehlich, R. Young, T.
Synthesis of the Cobalt(II) Salt of COOH-POSS (COOCo-POSS):
This material was prepared according to the procedure described
for COOCu-POSS. A purple solid was obtained in 95% yield. EDS
analysis (atomic): Na/Si = 0 and Co/Si = 0.49.
Eur. J. Inorg. Chem. 2012, 143–150
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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