triazole ring), 2.23 (td, J ~ 7.8 Hz, J ~ 2.5 Hz, 2H, CH2 in b of
Mathur, D. F. Bocian, V. Misra and J. S. Lindsey, J. Org. Chem., 2004,
69, 1444; (b) alcohol or alkene substituent/surface Si–H, Z. Liu, A. A.
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J. M. Tour, Chem. Mater., 2007, 19, 4447.
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∫
∫
CH), 1.95 (t, J ~ 2.5 Hz, 1H, CH), 1.7–1.5 (m, 6H, 3 CH2). MS
(ESI) m/z: 832 (M + H+).
Functionalisation procedures
Step 1: formation of the alkyne-terminated Si(100) surface
(surface 2). The silicon sample was first rinsed with acetone and
ethanol. It was then dipped in hot piranha solution (100 ◦C, 1 vol
30% by weight aqueous hydrogen peroxide to 2 vol sulfuric acid)
and etched in HF solution (1 vol 40% by weight hydrofluoric acid
diluted with 5 vol water). After 3 piranha–HF cycles, the silicon
wafer was transferred to a reaction vial containing freshly distilled
1,8-nonadiyne (which was degassed through a minimum of
4 freeze–pump–thaw cycles). The reaction vial was heated at
140 ◦C overnight under a stream of argon. The functionalised
surface was rinsed sequentially with copious amounts of chloro-
form, ethyl acetate and ethanol before being either analysed or
further reacted with substituted azide species.
Step 2: preparation of the porphyrin-terminated Si(100) surface
(surface 3). To a reaction vial containing the alkyne-terminated
silicon surface (which was immersed in 10 mL of DMF) were
added 4 (60 mg, 0.1 mmol), CuSO4·5H2O (2.5 mg, 0.01 mmol) and
ascorbic acid (8 mg, 0.05 mmol). The reaction vial was heated at
50 ◦C for 24 h. The functionalised surface was rinsed sequentially
with copious amounts of ethyl acetate, ethanol and water before
being analysed.
8 (a) R. Huisgen, Angew. Chem., Int. Ed. Engl., 1963, 2, 565; (b) H. C.
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3903.
Acknowledgements
We are grateful to Olivier Renault for XPS analyses, to Ne´vine
Rochat and Christophe Licitra for FTIR and ellipsometry anal-
yses and to Pierre-Alain Bayle for NMR experiments. Support
from the ‘Carnot’ program of the CEA-LETI is gratefully
acknowledged.
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16 Although elucidation of the chemical nature of the Si–alkyne bonding
was outside the scope of this work, we note that Si–H hydrosilylation
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reacts with an adjacent Si–H group.7a In our case the absence of C C
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3798 | Dalton Trans., 2009, 3793–3799
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