pubs.acs.

org/Langmuir XXXX American Chemical Society

Preparation of Covalent Long-Chain Trialkylstannyl and Trialkylsilyl Salts and an Examination of their Adsorption on Gold
Dushant Khobragade, Elizabeth S. Stensrud, Mazgorzata Mucha, Joshua R. Smith, Radek Pohl, Ivan Stibor, and Josef Michl*,,
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nm. 2, 166 10 Prague 6, Czech Republic, and Department of Chemistry and Biochemistry, a University of Colorado, Boulder, Colorado 80309-0125

Received March 12, 2010

We report the attachment of alkyl residues to a gold surface through a tin atom. Covalent trialkylstannyl and trialkylsilyl salts of trifluoromethanesulfonic, trifluoroacetic, and p-toluenesulfonic acids containing one to three C18H37 chains and two to no CH3 groups in the molecule have been synthesized. They were tested for adsorption on gold from solution under ambient conditions using ellipsometry, FTIR spectroscopy, contact angle, and electrode-blocking measurements. All nine trialkylstannyl salts form similar stable monolayers with the loss of the acid residue and form no multilayers. The monolayers differ from those formed from alkanethiols. They are much thinner, less ordered, less hydrophobic, and only slightly electrode-blocking. Their stability to solvents, bases, acids, and reductants is somewhat lower than that of a 1-octadecanethiol monolayer, but their resistance to heat and oxidants, including air, is slightly better. The distinctive properties of these monolayers may be of interest in certain circumstances, but we expect the attachment of molecules to gold through a tin atom to be of the most value in work with single-molecule structures. The trialkylsilyl salts showed no tendency to adsorb onto gold under these conditions.

Introduction
The attachment of isolated molecules and the formation of selfassembled monolayers (SAMs) on gold and other metal surfaces through a divalent sulfur atom are facile and well documented.1-3 This type of attachment has many advantages, especially ease of formation under ambient conditions, but it also has certain shortcomings. In particular, the limited long-term stability of thiolates to oxidation in air,4-6 and the relatively poor electronic communication through the electronegative sulfur atom restrict their use in certain applications where single molecules need to be attached to metal surfaces, as in molecular electronics. It appears desirable to find alternative modes of single-molecule attachment to metal surfaces, but efforts in this direction have been limited. In addition to the attachment through the sulfur atoms of dithiocarbamates,7 the formation of SAMs on gold from solution
(1) Love, J. C.; Estroff, L. A.; Kriebel, J. K.; Nuzzo, R. G.; Whitesides, G. M. Chem. Rev. 2005, 105, 1103. (2) Ulman, A. Chem. Rev. 1996, 96, 1533. (3) Ulman, A. Ultrathin Organic Films; Academic Press: San Diego, 1991. (4) Joseph, Y.; Guse, B.; Nelles, G. Chem. Mater. 2009, 21, 1670. (5) Willey, T. M.; Vance, A. L.; van Buuren, T.; Bostedt, C.; Terminello, L. J.; Fadley, C. S. Surf. Sci. 2005, 576, 188. (6) Huang, F. K.; Horton, R. C; Myles, D. C., Jr; Garrell, R. L. Langmuir 1998, 14, 4802. (7) Morf, P.; Raimondi, F.; Nothofer, H.-G.; Schnyder, B.; Yasuda, A.; Wessels, J. M.; Jung, T. A. Langmuir 2006, 22, 658. (8) Shaporenko, A.; Ulman, A.; Terfort, A.; Zharnikov, M. J. Phys. Chem. B 2005, 109, 3898. (9) Monnell, J. D.; Stapleton, J. J.; Jackiw, J. J.; Dunbar, T.; Reinerth, W. A.; Dirk, S. M.; Tour, J. M.; Allara, D. L.; Weiss, P. S. J. Phys. Chem. B. 2004, 108, 9834. (10) Clark, B. K.; Standard, J. M.; Gregory, B. W.; Hall, A. D. Surf. Sci. 2002, 498, 285. (11) Samant, M. G.; Brown, C. A.; Gordon, J. G., II. Langmuir 1992, 8, 1615. (12) Protsailo, L. V.; Fawcett, W. R.; Russell, D.; Meyer, R. L. Langmuir 2002, 18, 9342. (13) Han, S. W.; Kim, K. J. Colloid Interface Sci. 2001, 240, 492. (14) Weidner, T.; Shaporenko, A.; Mueller, J.; Hoeltig, M.; Terfort, A.; Zharnikov, M. J. Phys. Chem. C 2007, 111, 11627.

or vapor has been limited to attachment through selenium,6,8-13 tellurium,14 and silicon15-17 atoms and through the carbon atoms of acetylenes,18 diazonium salts,19,20 and isocyanides.21 The present work follows up on observations22-24 of the adsorption of trifluoroacetate salts of certain organomercuryl cations on gold, accompanied by the loss of the trifluoroacetate anion. In those experiments, a tetraarylcyclobutadienecobaltcyclopentadienyl sandwich complex carrying five HgOCOCF3 substituents on its five-membered ring and a similar compound containing two such derivatized metal sandwich complexes joined through a polycyclic aromatic bridge were adsorbed on a gold surface. Infrared and X-ray photoelectron spectroscopy measurements provided evidence that the adsorption of the metal sandwich complex was mediated by the interaction of the Hg atom with the gold surface. This intriguing observation prompted us to investigate whether such adsorption occurs for other organometallic salts and whether it could be generally useful for the attachment of organic molecules to metal surfaces. The electropositive nature of the ligand atom might be favorable for electronic communication. This article reports the synthesis of a series of
(15) Owens, T. M.; Suezer, S.; Banaszak Holl, M. M. J. Phys. Chem. B 2003, 107, 3177. (16) Owens, T. M.; Nicholson, K. T.; Banaszak Holl, M. M.; Suezer, S. J. Am. Chem. Soc. 2002, 124, 6800. (17) Katsonis, N.; Marchenko, A.; Taillemite, S.; Fichou, D.; Chauraqui, D.; Aubert, C.; Malacria, M. Chem.;Eur. J. 2003, 9, 2574. (18) Zhang, S.; Chandra, K. L.; Gorman, C. B. J. Am. Chem. Soc. 2007, 129, 4876. (19) Shewchuk, D. M.; McDermott, M. T. Langmuir 2009, 25, 4556. (20) Laforgue, A.; Addou, T.; Belanger, D. Langmuir 2005, 21, 6855. (21) Stapleton, J. J.; Daniel, T. A.; Uppili, S.; Cabarcos, O. M.; Naciri, J.; Shashidhar, R.; Allara, D. L. Langmuir 2005, 21, 11061. (22) Zheng, X.; Mulcahy, M. E.; Horinek, D.; Galeotti, F.; Magnera, T. F.; Michl, J. J. Am. Chem. Soc. 2004, 126, 4540. (23) Mulcahy, M. E.; Magnera, T. F.; Michl, J. J. Phys. Chem. C 2009, 113, 20698. (24) Mulcahy, M. E.; Bastl, Z.; Stensrud, K. F.; Magnera, T. F.; Michl, J., submitted for publication.

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RR0 R00 MX compounds, where one to three alkyl groups R are octadecyl and the others are methyl, M is tin or silicon, and X is a leaving group (triflate, trifluoroacetate, or tosylate). The formation and stability of SAMs on gold was monitored by ellipsometry, infrared spectroscopy, contact angle, and electrode-blocking measurements.

Results
Synthesis. Trialkylstannyl Salts. Tetraalkyltin compounds 2,25 3, and 4 were synthesized from commercial tin chlorides and the corresponding Grignard reagent.

Tin triflates (5a, 6a, and 7a), trifluoroacetates (5b, 6b, and 7b), and tosylates (5c, 6c, and 7c) were prepared by refluxing tetraalkylstannanes 2-4 with the corresponding acid in dichloromethane solution26 (Scheme 1). A slight excess of trifluoroacetic acid was used to compensate for its volatility.
Scheme 1. Synthesis of Stannyl Salts

Trialkylsilyl Salts. (See the Supporting Information.) Aryloctadecylsilanes were prepared according to the procedure developed by Gilman et al.27 1-Bromooctadecane was converted to octadecylmagnesium bromide and treated with neat chlorosilane to obtain silanes 8-14. Most of the chlorosilanes were commercially available, and p-anisyltrichlorosilane was synthesized as reported by Powell and Fu.28

Monoarylsilanes 8-10 and 14 were converted into solutions of covalent triflate or trifluoroacetate salts by protodesilylation with 1 equiv of the corresponding acid.29 Excess acid was required when more than one phenyl group was present (11-13).30 The resulting solutions were characterized by NMR spectroscopy and were tested for adsorption on a gold surface, but no attempt was made to isolate the neat salts. Product Structure. One of the tetraalkylstannanes was known (225), and the analytical data for the others were in agreement with a tetrahedral arrangement around the tin atom (3 and 4). The situation is more complicated for salts 5-7. The 119Sn NMR chemical shifts for CDCl3 solutions of such stannyl salts have values ranging from 75 to 165 ppm, and this is regarded as typical
(25) Meals, R. N. J. Org. Chem. 1944, 9, 211. (26) Sasin, G. S.; Borror, A. L.; Sasin, R. J. Org. Chem. 1958, 23, 1366. (27) Gilman, H.; Miles, D. H.; Moore, L. O.; Gerow, C. W. J. Org. Chem. 1959, 24, 219. (28) Powell, D. A.; Fu, G. C. J. Am. Chem. Soc. 2004, 126, 7788. (29) Hbich, D.; Effenberger, F. Synthesis 1978, 755. a (30) Schmeisser, M.; Sartori, P.; Lippsmeier, B. Chem. Ber. 1970, 103, 868.

of a quasitetrahedral arrangement in trimethyltin(IV) compounds with a four-coordinate tin atom.31 All trifluoroacetates (5b, 6b, and 7b), triflate 6a, and tosylate 7c belong in this category. Triflate 5a was measured in THF, and the strong upfield shift (200 ppm) is characteristic of the formation of a five-coordinate complex with solvent donor molecules.32 The spectral data of compounds 5-7 are summarized in Table 1. We were unable to detect 119Sn signals for tosylates 5c and 6c and triflate 7a. Adsorption on Gold. Tests for the formation of monolayers were performed under ambient conditions by immersing a goldcoated glass surface into a solution of a stannyl or silyl salt for several hours, followed by rinsing and drying before examination by ellipsometry, contact angle, FTIR spectroscopy, and electrochemistry. A cursory check gave discouraging results for the silyl salts, which showed little if any adsorption under these conditions. In contrast, trialkylstannyl salts 5-7 readily adsorbed onto gold substrates. Thereafter, we focused our efforts on characterizing the formation of the trialkylstannyl monolayers and their comparison with a standard 1-octadecanethiol (1) monolayer and have postponed further investigation of the silyl salts, which may yet show adsorption under different conditions. Ellipsometry. Figure 1 shows the gradual increase in the ellipsometric thickness of a surface layer when a gold substrate is immersed in a solution of trialkylstannyl salts 5-7. The adsorption is self-limiting, and the growth of the adsorbed layer stops after about an hour under the conditions used. It appears that the tosylates form an adsorbed layer the fastest, but we have detected no significant difference in the ultimate thickness nor in any other properties of the layers formed from the stannyl triflates, trifluoroacetates, and tosylates (Figure 1A). It seems that the compounds carrying only one long alkyl chain on the tin atom adsorb the fastest, but once again, the number of long chains on the tin atom has little if any effect on the final observed ellipsometric thickness (Figure 1B). The limiting ellipsometric thickness reported in Figure 2A for the adsorbed layers of alkylstannyl derivatives 5-7 (6 to 7 A) and of 1-octadecanethiol (1) (22 A) has only relative significance because we do not know the optical constants of the trialkylstannyl structures. The values were determined with the refractive index assumed to be 1.47, a value typical of tetraalkylstannanes with relatively short alkyl chains.25 Contact Angles. Contact angles of water on trialkylstannyl monolayers 5-7 were 92-97, distinctly higher than the 71 ( 3.5 measured on the clean gold substrate and distinctly lower than the 113 observed for a 1-octadecanethiol monolayer (Figure 2B). There was again no significant dependence on the nature of the leaving group or the number of long chains on the tin atom. FTIR Spectroscopy. Single-reflection attenuated total reflectance (ATR) Fourier transform infrared spectroscopy was used to confirm the presence of the monolayers on the gold surface. The recorded IR spectra of 5-7 on gold show only vibrations attributable to the CH3 and CH2 groups (stretching at 2855, 2871, 2926, and 2961 cm-1 and bending at 1378, 1418, and 1468 cm-1), and no evidence of the typical peaks of the triflate, trifluoroacetate, or tosylate residues was detected. The C-H stretching vibration region between 2800 and 3000 cm-1 is particularly informative, and Figure 3 shows the spectra of 5-7 on gold, along with that of a 1-octadecanethiol (1) monolayer for comparison. For 5-7, the vas(CH2), vs(CH2), vas(CH3), and vs(CH3) bands are observed at 2926, 2855, 2961, and 2871 cm-1, respectively, regardless of the nature of the leaving group. The vs(CH3) band
(31) Kapoor, R.; Sood, V.; Kapoor, P. Polyhedron 1995, 14, 489. (32) Chandrasekhar, V.; Thirumoorthi, R. Eur. J. Inorg. Chem. 2008, 4578.

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Table 1. NMR Data for Stannyl Salts 5-7a
compound 5a 119Sn/ ppm -15.75 1H/ppm (499.8 MHz): 0.89 (t, J = 7 Hz, 9H), 1.29 (bs, 92H), 13C/ppm

Article

19F/ppm -75.16 -71.02

(125.7 MHz): -14.63, 20.78, 23.73, 26.56, 30.35, 30.49, 30.79, 30.80, 30.83, 30.85, 30.86, 35.15, 121.07, (q, JC-F = 319.1 Hz) 5b 172.31 (499.8 MHz): 0.88 (t, J = 7.0 Hz, 9H), (125.7 MHz): 14.11, 17.71, 22.70, 25.36, 29.14, 1.20-1.36 (m, 90H), 1.40 (m, 6H), 1.67 (m, 6H) 29.39, 29.52, 29.65, 29.68, 29.72, 29.73, 31.94, 33.99, 115.18, (q, JC-F = 288.1), 161.33, (q, JC-F = 39.9). b (499.8 MH): 0.89 (t, J = 6.8 Hz, 9 H), 5c (125.7 MHz): 14.11, 20.55, 21.37, 22.70, 1.10-1.35 (m, 96H), 1.49 (bm, 6H), 2.36 25.53, 29.41, 29.70, 29.71, 29.78, (s, 3H), 7.16 (m, 2H), 7.60 (m, 2H). 29.79, 29.82, 29.84, 29.86, 29.89, 31.95, 34.12, 126.06, 128.98, 139.46, 141.61 6a 160.74 (600.1 MHz): 0.70 (s, 3H), 0.88 (t, J = 7.0 Hz, 6H), (150.9 MHz): -0.20,14.12, 21.39, 22.70, 1.22-1.38 (m, 60H), 1.41 (m, 4H), 1.68 (m, 4H) 25.14, 29.22, 29.39, 29.65, 29.69, 29.75, 29.76, 29.77, 29.78, 31.94, 33.72, 118.80, (q, JC-F 317.8). 6b 183.89 (499.8 MHz): 0.62 (s, 3H), 0.88 (t, J = 7.1 Hz, 6H), (125.7 MHz): -3.88, 14.11, 18.17, 1.21-1.35 (m, 60H), 1.42 (m, 4H), 1.67 (m, 4H). 22.70, 25.23, 29.11, 29.37, 29.49, 29.63, 29.65, 29.67, 29.71, 31.93, 33.79, 115.12, 161.24 b (499.8 MHz): 0.56 (s, 3H), 0.89 (t, J = 6.9 Hz, 6H), (125.7 MHz): -0.32, 14.11, 21.10, 6c 1.10-1.35 (m, 64H), 1.48 (m, 4H), 2.37 21.38, 22.70, 25.43, 29.39, 29.70, (s, 3H), 29.76, 29.78, 29.80, 29.82, 29.84, 7.17 (m, 2H), 7.56 (m, 2H). 29.86, 31.94, 33.91, 125.95, 129.05, 139.38, 141.77. b (499.8 MHz): 0.75 (s, 6H), 0.88 (t, J = 7 Hz, 3H), (125.7 MHz): 0.82, 14.11, 21.56, 22.69, 7a 1.21-1.38 (m, 30H), 1.42 (m, 2H), 1.68 (m, 2H) 24.99, 29.15, 29.37, 29.58, 29.67, 29.70, 29.72, 29.73, 31.93, 33.47, 118.67 (q, JC-F = 317.5) 7b 192.57 (499.8 MHz): 0.63 (s, 6H), 0.84 (t, J = 7.0 Hz, 3H), (125.7 MHz): -2.69, 14.12, 18.52, 22.69, 1.20-1.30 (m, 30H), 1.41 (m, 2H), 1.65 (m, 2H). 25.14, 29.08, 29.36, 29.46, 29.60, 29.63, 29.66, 29.69, 31.92, 33.63, 115.04, 161.18. 7c 83.08 (499.8 MHz): 0.56 (s, 6H), 0.88 (t, J = 6.8 Hz, 3H), (125.7 MHz): 0.77, 14.10, 21.24, 21.39, 1.10-1.33 (m, 32H), 1.46 (bm, 2H), 2.38 (s, 3H), 22.68, 25.29, 29.31, 29.37, 29.64, 7.19 (m, 2H), 7.55 (m, 2H). 29.68, 29.73, 29.75, 29.76, 29.78, 31.92, 33.67, 125.30, 129.14, 139.09, 142.00. a In CDCl3 solvent in all cases except 5a in THF-d8. b No 119Sn NMR signal found.

-78.25

-71.05

-74.04

-71.09

is weak in the spectrum of 1 and present only as an indistinct shoulder in the spectra of 5-7. Electrode-Blocking Properties. To provide information about the permeability of the adsorbed layers, we measured their electrochemical blocking properties by cyclic voltammetry (CV) using the [Fe(CN)6]3-/[Fe(CN)6]4- system as a redox probe. Figure 4 compares the responses to 2 mM [Fe(CN)6]3- in 0.1 M KCl observed on a bare gold electrode and on an electrode that had been immersed for 2 h in a solution of a trialkylstannyl tosylate. The adsorbed layer reduces the current response relative to the bare electrode, especially when the tin atom carries three long chains, but blocking is not complete even after immersion overnight. In contrast, a SAM of 1 suppresses the electrochemical response essentially completely, and only the charging current remains. Monolayer Stability. The stability of the trialkylstannyl adsorbed layers was examined under a variety of conditions by monitoring the loss of their IR absorbance between 2800 and 3000 cm-1 as a function of time after exposure either to the laboratory atmosphere for a week or to various solvents for 15-18 h, followed by thorough rinsing and drying. The results for the trialkylstannyl monolayers were compared with those obtained for a SAM built from 1-octadecanethiol (1). Numerous initial tests with all three leaving groups showed that they all gave identical results, and those shown in Figure 5 were obtained with tosylates as averages of at least three measurements. Even in the cases in which the monolayers were partially or fully desorbed, we did not observe the appearance of any new absorption bands. After extended exposure to H2O2, the gold substrates appeared to be pitted. In Figure 6, we show the time dependence of the loss of
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IR intensity for the adsorbed layer of 7 in water, ethanol, methylene chloride, and hydrogen peroxide. Thermal Desorption. The thermal desorption of the trialkylstannyl monolayers was followed by keeping the monolayer under nitrogen for 1 h each at 80, 140, and finally 200 C, rinsing with ethanol, and observing the decrease in overall IR signal intensity (Figure 7). No IR spectral shape changes resulted for the monolayers of 5-7, but the spectrum of the SAM of 1 changed after heating to 80 C and became essentially identical with the spectra of 5-7.

Discussion This article describes an effort to expand the options available for attaching organic molecules directly to metal surfaces under ambient solution conditions. Until now, such attachment relied on the surface bonding of an atom Z carrying one organic group R such as an alkyl or an aryl and has yielded surface structures of the type RZMn, where Mn stands for one or more atoms of the metal. Elements of group 16 in the periodic table, especially sulfur, represent the classical example of Z, and their electronegativity tends to endow the RZ-Mn bond or bonds with a Z-M polarity. The steric demands of a single alkyl are such that this approach permits the assembly of large domains of essentially impermeable, tightly packed layers of long alkane chains that are somewhat tilted from the surface normal. Even the reported attachment through a silicon atom,15-17 which works only under vapor deposition conditions, uses monoalkylsilanes and attaches a single organic group through each silicon atom. Since the formation of impermeable
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Figure 3. ATR-FTIR spectra of 1 (black line), 5 (purple lines), 6 (gold lines), and 7 (blue lines) adsorbed on gold. From top to bottom, successively shifted by 0.01 absorbance units: 1, 7a, 7b, 7c, 6a, 6b, 6c, 5a, 5b, and 5c.

Figure 1. Kinetics of monolayer formation at room temperature for 5-7 compared with that of 1-octadecanethiol (1, 1). (A) Effect of the leaving group: triflate7a (gray pentagon), trifluoroacetate 7b (turquoise triangle), and tosylate 7c (blue square). (B) Effect of the number of long chains on the Sn atom in tosylates 5c (purple triangle), 6c (orange circle), and 7c (blue square).

Figure 4. Cyclic voltammograms at 100 mV/s of Fe(CN)63-/4- on a bare gold electrode (gray line) and an electrode with an adsorbed layer of 1 (black line), 5c (purple line), 6c (orange line), and 7c (blue line) after 2 h of immersion.

Figure 5. Stability of adsorbed monolayers of 1 (black bars), 5 (purple bars), 6 (orange bars), and 7 (blue bars) to overnight immersion in various reagents at room temperature, followed by rinsing and drying. R is the percent monolayer remaining on the gold surface, calculated as the ratio of the final to the initial integrated intensity of the 2800-3000 cm-1 bands. (A) Dry CH2Cl2, (B) wet CH2Cl2, (C) n-hexane, (D) ethanol, (E) water, (F) 0.1 M H2SO4, (G) 0.1 M NaOH, (H) 1 mM KMnO4, (I) 30% H2O2, (J) 10 mM NaBH4, and (K) 7 days in laboratory air.

Figure 2. (A) Ellipsometric thickness and (B) static contact angle of

water on adsorbed layers of 1 and 5-7 on gold after 2 h of immersion.

layers often is the objective of surface modification, RZH and RZZR (or RSiH3) reagents serve the purpose admirably. They have also been used when the attachment of isolated single
D DOI: 10.1021/la101023b

molecules rather than the formation of a continuous layer is the desired goal, as in measurements of single-molecule conductivity in break junctions. In this case, the two principal disadvantages of the use of elements of group 16 come to the forefront. Structure RZMn is relatively easily oxidized in laboratory air,33 which tends to
(33) Schoenfisch, M. H; Pemberton, J. E. J. Am. Chem. Soc. 1998, 120, 4502.

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Figure 6. Temporal degradation of monolayer 7c upon exposure to reagents. Dry CH2Cl2 (A, black), ethanol (D, orange), water (E, green), and 30% H2O2 (I, purple). R is the percent monolayer remaining on the gold surface, calculated as the ratio of the final to the initial integrated intensity of the 2800-3000 cm-1 bands.

Figure 7. Thermal desorption of monolayers of 1 (black bars), 5c (purple bars), 6c (orange bars), and 7c (blue bars) on gold after 1 h at 20, 80, 140, and 200 C. (A) IR spectra of adsorbed 1 (black) and 7c (blue), starting from the top. (B) Percent of adsorbed layer remaining on the gold surface, calculated as the ratio R of the final to the initial integrated intensity in the 2800-3000 cm-1 region.

contain traces of ozone, and the transport of electrons across the partially polar Z-M bond is relatively difficult. As mentioned in the Introduction, an accidental observation of adhesion of organomercuryl cations to gold, accompanied by the loss of the counterion and thus presumably due to the reductive formation of an Hg-Aun bond or bonds, prompted us to ask whether divalent elements from group 12 might not generally work as well as elements of group 16 and also yield structures of the type RZMn. They are much less electronegative and much less oxidizable and could form less polar and less readily oxidizable metal-metal bonds Z-M. The requisite reagents are not readily available in the form of RZH or RZZR but are easily accessible in
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the form of salt RZX, where X is a leaving group such as a halogen or the anion of an oxyacid. Once we admit that Z does not need to be from group 16 but could be from group 12, it is natural to ask whether it could also be from groups 13-15. The useful stable valency for elements of groups 13 and 15 would be three, and if one wished to have a single organic substituent, the reagent to try would be RZX2. For elements of group 14, the useful valency could be four or two, suggesting the use of RZX3 and RZX. However, if a tightly packed monolayer is not the objective, then there is no reason to limit the number of organic residues attached to Z to one, and structures R2ZX with Z from group 13 or 15, R3ZX with Z from group 14, and R2ZX3, R2(O)ZX, or R2(S)ZX with Z from group 15 become interesting possibilities. Even for the smallest R groups, there will be considerable congestion in a monolayer if one tries to accommodate two or three such groups at each atom Z and these atoms will have to be spaced relatively far apart. One can then anticipate much more disordered and more permeable layers, which might have new uses. For instance, the affinity of such layers for organic and other vapors could be considerable, and they might find use in sensors. Since the number of suitable elements in groups 12-15 is large and the two or three organic residues attached to Z need not be the same, the number of structural possibilities is daunting. We have started to examine a few of them and presently report that under ambient conditions adsorption from solution does not take place readily for R3ZX when Z = Si but occurs readily when Z = Sn. There is currently no direct evidence for the nature of the surface bond, and in the following discussion, we make the reasonable assumption that the Sn atom of the R3Sn group is attached to the gold surface through an Sn-Au or Sn-Aun bond. The following aspects of the results for the trialkylstannyl monolayers strike us as interesting. (i) There is no indication that leaving group X stays in the monolayer. It is apparently released in the adsorption event, most likely as anion X-, and its nature plays no role in determining the properties of the resulting adsorbed layer. This agrees with the expectation that its structure indeed is R3Sn-Au or R3Sn-Aun. If the leaving group departs in the form of an anion, then it is likely that the electron needed to form X- as the R3Sn residue is being attached to the surface is obtained from the metal, but there is no direct evidence for this assumption. (ii) The results obtained in this article show that the monolayers formed are quite disordered and much thinner than the SAM formed from 1-octadecanethiol. This is apparent in the lower contact angles for water, in the poor electrode-blocking properties, in the lower resistance to removal by solvents, in the ellipsometric thickness, and in the IR spectra. The symmetric CH2 stretch occurs at 2855 cm-1, 7 cm-1 above, and the antisymmetric CH2 stretch occurs at 2926 cm-1, 6 cm-1 above their respective locations in the highly ordered SAM of 1-octadecanethiol (1). Upon heating to 80 C under an inert atmosphere, the SAM formed from 1 becomes disordered and the symmetric and antisymmetric CH2 stretches move to higher frequencies. In the monolayers formed from 5-7, these bands are already shifted at room temperature and no further shift occurs upon heating (Figure 7). Thermal desorption of the monolayers is a little easier for the trialkylstannyl monolayers than for that formed from 1 at 80 C, but the difference is small and at higher temperatures the SAM of 1 actually desorbs faster. (iii) The stabilities of the trialkylstannyl monolayers to chemical reagents are generally lower than those of the SAM formed from 1. This may be due primarily to their higher permeability, which is particularly clearly demonstrated by the electrodeblocking experiments (Figure 4). The trialkylstannyl monolayers
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appear to be stable in solvents such as n-hexane and ethanol, whereas after 15 h in methylene chloride (both dry and wet) or water nearly 50% of the monolayers of 5-7 are removed from the gold surface (Figure 5). Desorption of the alkylstannyl monolayers was also observed in strong aqueous base. Surprisingly, after extended exposure to aqueous acid 80-90% still remain on the gold surface. The alkylstannyl monolayers generally resist oxidants better than the SAM of 1. This is especially true of hydrogen peroxide, but even their stability in ambient air seems to be a little better. In a solution of strong reducing agent NaBH4, all monolayers remain intact. It is quite likely that the resistance of all of these adsorbed monolayers to removal by solvents is sensitive to details of their preparation and annealing, particularly domain structure, since monolayer destruction may start at interdomain boundaries. We are not proposing that the results shown in Figure 5 have absolute validity, but they are reproducible and are likely to provide relative stability information for the particular set of monolayer preparation conditions that we have used. (iv) The properties of the trialkylstannyl monolayers built from molecules containing one, two, or three long chains are nearly identical, and only the electrode blocking shows some differentiation. This similarity extends to the ellipsometric thickness, but this result may be somewhat misleading since the index of refraction is likely to increase a little in the order of 7, 6, and 5. In any event, although the 6 to 7 A thickness suggested by ellipsometry cannot be taken at face value, the fact that this number is only about 1/3 of that observed for the SAM built from 1 suggests very strongly that the long alkyl chains lie on the gold surface. The exact structure of these monolayers and the determination of their real thickness require further investigation. The surface density of tin atoms in the three types of layers will be particularly interesting to compare.

Conclusions
Trialkylstannyl salts appear suitable for the attachment of alkyl chains to a gold surface. The properties of the resulting disordered layers are quite different from those of the highly organized layers built from 1-octadecanethiol (1), and their structure remains to be determined.

Experimental Methods
Adsorbed Monolayer Formation. Glass substrates coated with 2000 A of gold were purchased from Platypus Technologies. Prior to use, they were cleaned in piranha solution (3:1 sulfuric acid/hydrogen peroxide) at 90 C, rinsed with copious amounts of 18.2 M H2O and absolute ethanol, and dried under a stream of nitrogen. Trialkylstannyl monolayers were formed by immersing the gold substrates in a 1 10-5 M solution of a trialkylstannyl salt in dry CH2Cl2 for 2 h. Monolayers of 1-octadecanethiol (1) were formed on the gold substrates by immersing the substrate in a 1 10-5 M solution in absolute ethanol for 2 h. After removal from solution, the gold substrates were rinsed thoroughly with either absolute ethanol or CH2Cl2 and dried under a stream of nitrogen prior to analysis. Silyl triflates or trifluoroacetates were dissolved in dry solvent (n-pentane or dichloromethane), and the solution was diluted to approximately 1 mM. The gold substrate was first treated with a solution of triflic anhydride for 1 day and rinsed with dichloromethane followed by hexane prior to immersion into the solution of silyl salts to avoid the formation of siloxanes.34 Subsequent analysis by ellipsometry, contact angle, and IR failed to reveal any evidence of the deposition of any material on the gold surface.
(34) Finklea, H. O.; Robinson, L. R.; Blackburn, A.; Richter, B.; Allara, D.; Bright, T. Langmuir 1986, 2, 239.

Stability of Monolayers. The 5-7 SAMs were prepared as described above, and the IR spectrum of each sample was recorded. For stability measurements, the gold slide was immersed for 15-18 h at room temperature in dry CH2Cl2, wet CH2Cl2, n-hexane, ethanol, water, 0.1 M H2SO4, 0.1 M NaOH, 1 mM KMnO4, 30% H2O2, or 10 mM NaBH4, removed from solution, rinsed thoroughly with either an appropriate solvent (CH2Cl2, hexane, or ethanol) or with copious amounts of 18.2 M H2O and absolute ethanol in the case of water solutions, and dried under a stream of nitrogen before an IR spectrum was recorded. The samples were also exposed to the ambient laboratory atmosphere for 7 days and then rinsed with absolute ethanol and dried before the IR spectrum was measured. The thermal desorption of the trialkylstannyl monolayers was followed by keeping the monolayer under nitrogen for 1 h each at 80, 140, and finally 200 C. Prior to the IR measurements, the gold slides were rinsed with absolute ethanol and dried under a stream of nitrogen. Ellipsometry. All measurements were made using a Variable Angle Stokes ellipsometer (Gaertner Scientific) with a 633 nm HeNe laser with the incident angle adjusted to 70. Optical constants of the gold substrates were taken for all freshly cleaned substrates. An index of refraction of 1.47 was assumed for the films. Ellipsometry measurements were taken at a minimum of five different areas on each sample. Contact Angle. A static contact angle for 18.2 M H2O was found with a CAM101 instrument (KSV Instruments) using a 1 to 2 L drop of water. Measurements were taken at a minimum of five different areas for each sample. Infrared Spectroscopy. FTIR-ATR spectra (1000 scans, 4 cm-1 resolution) were recorded using a Nicolet 6700 FT-IR spectrometer (Thermo Electron Corporation) with a liquid-N2cooled MCT detector in the range of 650-4000 cm-1. The data were collected with p-polarized light at 45 incidence using a Seagull variable-angle accessory (Harrick Scientific Inc.) and a Ge hemisphere (12.5 mm diameter). Prior to each measurement, the Ge crystal was cleaned with ethanol and a reference spectrum of the crystal in contact with air was measured. Electrochemistry. Electrochemical measurements were performed using an AutoLab PGSTAT302N potentiostat (Metrohm Autolab). Electrochemistry was carried out in a conventional three-electrode glass cell at room temperature. A gold electrode, either bare or carrying an adsorbed layer, a platinum wire, and a Ag/AgCl (saturated KCl) electrode were used as the working, auxiliary, and reference electrodes, respectively. The blocking experiments were performed with a 0.1 M KCl solution containing 2 mM K3[Fe(CN)6] purged with Ar before measurement. A scan rate of 100 mV/s was used in all measurements. The voltammograms remained unchanged during six cycles. The curve shown is from the sixth cycle. Synthesis. Methods. Materials were purchased from SigmaAldrich or Alfa Aesar and used as received unless otherwise specified. 1-Bromooctadecane was distilled over CaCl2; tetrahydrofuran (THF), toluene, and pentane were distilled over benzophenone ketyl; dichloromethane (DCM) and acetonitrile (ACN) were freshly distilled over CaH2 or P2O5, and trifluoromethanesulfonic acid was distilled over a small amount of P2O5. NMR spectra were measured on a Bruker 400 MHz Ultrashield, a Bruker Avance II 500 MHz, and a Bruker Avance II 600 MHz and referenced to the solvent signal. FTIR spectra were recorded on a Bruker Equinox 55. Melting points were taken with a Stuart SMP3 instrument or Kofler block and are uncorrected. Mass spectrometry data were obtained with an LTQ Orbitrap XL or LCQ Fleet (both Thermo Fisher Scientific) or a Q-TOF micro (Waters) or Reflex IV (Bruker Daltonics) instrument. Elemental analyses were carried out on a Perkin-Elmer 2400 II instrument. Tetraoctadecyltin (2).25 Mg turnings (0.96 g, 0.04 mol) and a catalytic amount of I2 were taken in a three-necked roundbottomed flask fitted with a reflux condenser. The flask was heated with a heat gun until purple vapors of I2 appeared. THF (20 mL)
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Khobragade et al. was added, followed by 1-bromooctadecane (13.6 mL, 0.04 mol), and the mixture was heated to reflux under an argon atmosphere for 5 h. After the mixture was cooled to room temperature, SnCl4 (0.7 mL, 0.006 mol) was added dropwise. The mixture was refluxed for 5 h and then stirred overnight at room temperature. Hexane (50 mL) was added, and the reaction mixture was washed with a saturated NH4Cl solution (15 mL), water (3 25 mL), and saturated NaCl solution (15 mL). The hexane layer was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to obtain a white solid that was crystallized from ethyl acetate (6.0 g, 90% yield), mp 47-49 C (lit.25 47 C). IR (KBr, cm-1): 2956, 2918, 2873, 2850, 1468, 1455, 1418, 1378, 1342, 721, 598, 513, 501. 1H NMR (499.8 MHz, CDCl3): 0.72 (m, 8H), 0.81 (t, J = 7 Hz, 12H), 1.05-1.35 (m, 120H), 1.41 (m, 8H). 13C NMR (125.7 MHz, CDCl3): 9.17, 14.13, 22.72, 27.02, 29.32, 29.41, 29.71, 29.74, 29.77, 31.97, 34.49. 119Sn NMR (186.4 MHz, CDCl3): -13.45. Elemental analysis: calcd for C72H148Sn: C 76.35, H 13.17; found: C 77.03, H 13.45. Dioctadecyldimethyltin (3). Mg turnings (0.76 g, 0.031 mol) and a catalytic amount of I2 were taken in a three-necked roundbottomed flask and heated with a heat gun until the purple color of I2 appeared. THF (20 mL) was added, followed by 1-bromooctadecane (10.84 mL, 0.03 mol). The mixture was heated to reflux for about 5 h, and a solution of Me2SnCl2 (2.5 g, 0.011 mol) in THF (5 mL) was added dropwise. The mixture was refluxed for 5 h and stirred overnight at room temperature. Hexane (50 mL) was added, and the reaction mixture was washed with a saturated NH4Cl solution (15 mL), water (3 25 mL), and a saturated NaCl solution (15 mL). The hexane layer was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to obtain a white solid that was crystallized from ethyl acetate (6.92 g, 93% yield), mp 39-41 C. IR (KBr, cm-1): 2955, 2917, 2871, 2849, 1472, 1463, 1452, 1440, 1421, 1413, 1377, 1193, 1186, 761, 729, 720, 526, 518. 1H NMR (499.8 MHz, CDCl3): 0.01 (s, 6H), 0.81 (m, 4H), 0.89 (t, J = 7 Hz, 6H), 1.21-1.35 (m, 60H), 1.49 (m, 4H). 13C NMR (125.7 MHz, CDCl3): -11.14, 10.50, 14.13, 22.72, 26.80, 29.31, 29.40, 29.68, 29.70, 29.75, 31.96, 34.18. 119Sn NMR (186.4 MHz, CDCl3): -2.98. HRMS-EI calcd for C37H77Sn (M - CH3): 641.5047; found: 641.5063. Elemental analysis: calcd for C38H80Sn: C 69.60, H 12.30; found: C 69.30, H 12.45. Octadecyltrimethyltin (4). Mg turnings (0.18 g, 7.53 10-3 mol) and a catalytic amount of I2 were placed in a three-neck round-bottomed flask that was then heated with a heat gun until the purple color of I2 appeared. THF (20 mL) was added, followed by 1-bromooctadecane (2.57 mL, 7.53 10-3 mol), and the mixture was heated to reflux for about 5 h. Then a solution of Me3SnCl (1.0 g, 5.02 10-3 mol) in THF (5 mL) was added dropwise. The mixture was refluxed for 5 h and stirred overnight at room temperature. Hexane (50 mL) was added, and the reaction mixture was washed with a saturated NH4Cl solution (15 mL), water (3 25 mL), and a saturated NaCl solution (15 mL). The hexane layer was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to obtain a semisolid. Purification by column chromatography furnished the product (1.66 g, 79% yield). IR (KBr, cm-1): 2956, 2923, 2852, 1466, 1455, 1444, 1433, 1417, 1378, 1200, 1188, 764, 731, 720, 525, 510. 1H NMR (499.8 MHz, CDCl3): 0.06 (s, 9H), 0.85 (m, 2H), 0.90 (t, J = 7.1 Hz, 3H), 1.23-1.37 (m, 30H), 1.52 (m, 2H). 13C NMR (125.7 MHz, CDCl3): -10.32, 11.15, 14.17, 22.78, 26.78, 29.38, 29.48, 29.74, 29.77, 29.80, 29.82, 32.04, 34.12. 119Sn NMR (186.4 MHz, CDCl3): -1.21. HRMS-APCI calcd for C21H46SnNa (M Na): 441.2525; found: 441.2647. Elemental analysis calcd for C21H46Sn: C 60.44, H 11.11; found: C 60.73, H 10.95. Trioctadecyltin Triflate (5a). Tetraoctadecyltin (1 g, 8.85 10-4 mol) was dissolved in warm, dry DCM, and a solution of CF3SO3H (0.025 g, 0.18 10-3 mol) in dry DCM (1 mL) was added dropwise, followed by a 48 h reflux. DCM was evaporated on a rotatory evaporator to obtain a white solid that was crystallized from DCM/ACN (0.82 g, 90% yield), mp 77 to 78 C. IR (KBr, cm-1): 2956, 2918, 2872, 2850, 1468, 1378, 1321,1261, 1203,
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Article 1097, 1025, 804, 721, 656, 632, 582, 518. 1H NMR (499.8 MHz, THF-d8): 0.89 (t, J = 7 Hz, 9H), 1.29 (bs, 92H). 13C NMR (125.7 MHz, THF-d8): -14.63, 20.78, 23.73, 26.56, 30.35, 30.49, 30.79, 30.80, 30.83, 30.85, 30.86, 35.15, 121.07, (q, JC-F = 319.1). 19F NMR (470.3 MHz, THF-d8): -75.16. 119Sn NMR (186.4 MHz, CDCl3): -15.75. HRMS-ESI calcd for C54H111Sn (M - OTf): 879.7702; found: 879.7713. Elemental analysis: calcd for C55H111F3O3SSn: C, 64.24; H, 10.88; F, 5.54; S, 3.12; found: C 64.33; H 10.76, F 5.97, S 3.47. Trioctadecyltin Trifluoroacetate (5b). Tetraoctadecyltin (1 g, 8.83 10-4 mol) was dissolved in warm DCM (10 mL). A solution of trifluoroacetic acid (0.15 g, 1.33 10-3 mol) was added dropwise from a syringe. The mixture was refluxed for 48 h. An aliquot was removed, and the product crystallized from DCM/ACN. The 119Sn NMR spectrum showed that some starting material was still present. The reaction was continued, and again an aliquot was removed and the product crystallized from DCM/ACN. The 119Sn NMR spectrum showed the presence of some starting material. Then 0.5 equiv of trifluoroacetic acid was added, and the reaction was continued for 2 more days. An aliquot was removed, and the 119Sn NMR spectrum of the product showed no indication of the presence of the starting material. The reaction mixture was concentrated under reduced pressure, the residue was dissolved in DCM, and ACN was added. A pale yellow solid was obtained (0.81 g, 92% yield), mp 7072 C. IR (KBr, cm-1): 2956, 2919, 2850, 1670, 1650, 1468, 1379, 1213, 1191, 1159, 852, 840, 795, 728, 696, 675, 605, 523, 475. 1H NMR (499.8 MHz, CDCl3): 0.88 (t, J = 7.0 Hz, 9H), 1.20-1.36 (m, 90H), 1.40 (m, 6H), 1.67 (m, 6H). 13C NMR (125.7 MHz, CDCl3): 14.11, 17.71, 22.70, 25.36, 29.14, 29.39, 29.52, 29.65, 29.68, 29.72, 29.73, 31.94, 33.99, 115.18, (q, JC-F = 288.1), 161.33, (q, JC-F = 39.9). 19F NMR (470.3 MHz, CDCl3): -71.02. 119Sn NMR (186.4 MHz, CDCl3): 172.31. HRMSAPCI calcd for C54H77Sn (M - CCOCF3): 879.7702; found: 879.7719. Elemental analysis: calcd for C56H111F3O2Sn: C 67.79; H 11.28; F 5.74; found: C 68.16; H 11.56; F 6.11. Trioctadecyltin Tosylate (5c). A mixture of tetraoctadecyltin (1 g, 0.88 10-3 mol) and p-toluenesulfonic acid (0.152 g, 0.88 10-3 mol) was refluxed in DCM (10 mL) for 48 h. The reaction mixture was concentrated under reduced pressure to obtain a thick liquid, which was dissolved in hot ethyl acetate and left overnight. A white solid precipitated and was filtered off and dried overnight under reduced pressure at 60 C. A white solid was obtained (0.90 g, 98% yield), mp 56-58 C. IR (KBr, cm-1): 2955, 2919, 2850, 1601, 1497, 1468, 1378, 1194, 1131, 1044, 1015, 815, 721, 694, 569. 1H NMR (499.8 MHz, CDCl3): 0.89 (t, J = 6.8 Hz, 9 Hz), 1.10-1.35 (m, 96H), 1.49 (bm, 6H), 2.36 (s, 3H), 7.16 (m, 2H), 7.60 (m, 2H). 13C NMR (125.7 MHz,CDCl3): 14.11, 20.55, 21.37, 22.70, 25.53, 29.41, 29.70, 29.71, 29.78, 29.79, 29.82, 29.84, 29.86, 29.89, 31.95, 34.12, 126.06, 128.98, 139.46, 141.61. HRMS-APCI calcd for C54H111Sn (M - OTs): 879.7702; found: 879.7697. Elemental analysis: calcd for C61H118O3SSn: C 69.75; H 11.32; S 3.05; found: C 70.16; H 11.76; S 2.83. Dioctadecylmethyltin Triflate (6a). Yield 73%, mp 5658 C. IR (KBr, cm-1): 2954, 2917, 72850, 1468, 1414, 1378, 1257, 1179, 1034, 769, 721, 654, 644, 581, 523. 1H NMR (600.1 MHz, CDCl3): 0.70 (s, 3H), 0.88 t, J = 7.0 Hz, 6H), 1.22-1.38 (m, 60H), 1.41 (m, 4H), 1.68 (m, 4H). 13C NMR (150.9 MHz, CDCl3): -0.20,14.12, 21.39, 22.70, 25.14, 29.22, 29.39, 29.65, 29.69, 29.75, 29.76, 29.77, 29.78, 31.94, 33.72, 118.80, (q, JC-F = 317.8). 19 F NMR (376.5 MHz, CDCl3): -78.25. 119Sn NMR (186.4 MHz, CDCl3): 160.74. HRMS-ESI calcd for C37H77Sn (M OTf): 641.5042; found: 641.5049. Elemental analysis: calcd for C38H77F3O3SSn: C 57.79; H 9.83; F 7.22, S 4.06; found: C 57.74; H 10.11; F 7.30; S 4.02. Dioctadecylmethyltin Trifluoroacetate (6b). Yield 82%, mp 60-62 C. IR (KBr, cm-1): 2955, 2919, 2850, 1670, 1650, 1468, 1378, 1194, 1158, 854, 840, 796, 728, 672, 604, 536, 473. 1H NMR (499.8 MHz, CDCl3): 0.62 (s, 3H), 0.88 t, J = 7.1 Hz,
DOI: 10.1021/la101023b

Article 6H), 1.21-1.35 (m, 60H), 1.42 (m, 4H), 1.67 (m, 4H). 13C NMR (125.7 MHz, CDCl3): -3.88, 14.11, 18.17, 22.70, 25.23, 29.11, 29.37, 29.49, 29.63, 29.65, 29.67, 29.71, 31.93, 33.79, 115.12, 161.24. 19 F NMR (470.3 MHz, CDCl3): -71.05. 119Sn NMR (186.4 MHz, CDCl3): 183.89. HRMS-EI calcd for C38H74F3O2Sn: 739.4663; found: 739.4639. Elemental analysis: calcd for C39H77F3O2Sn: C 62.15; H 10.30; F 7.56; found: C 62.31; H 10.55; F 7.27. Dioctadecylmethyltin Tosylate (6c). Yield 85%, mp 39-41 C. IR (KBr, cm-1): 2954, 2917, 2850, 1601, 1468, 1378, 1192, 1132, 1045, 1015, 815, 720, 695, 607, 568, 525. 1H NMR (499.8 MHz, CDCl3): 0.56 (s, 3H), 0.89 (t, J = 6.9 Hz, 6H), 1.10-1.35 (m, 64H), 1.48 (m, 4H), 2.37 (s, 3H), 7.17 (m, 2H), 7.56 (m, 2H). 13C NMR (125.7 MHz, CDCl3) -0.32, 14.11, 21.10, 21.38, 22.70, 25.43, 29.39, 29.70, 29.76, 29.78, 29.80, 29.82, 29.84, 29.86, 31.94, 33.91, 125.95, 129.05, 139.38, 141.77. HRMS-APCI calcd for C37H77Sn (M OTs): 641.5042; found: 641.5042. Elemental analysis: calcd for C44H84O3SSn: C 65.09; H 10.43; S 3.95; found: C 65.27; H 10.68; S 3.65. Octadecyldimethyltin Triflate (7a). Yield 75%, mp 4951 C. IR (KBr, cm-1): 2952, 2915, 2849, 1470, 1376, 1258, 1179, 1039, 1034, 840, 768, 718, 655, 644, 580, 544, 520. 1H NMR (499.8 MHz, CDCl3): 0.75 (s, 6H), 0.88 (t, J = 7 Hz, 3H), 1.21-1.38 (m, 30H), 1.42 (m, 2H), 1.68 (m, 2H). 13C NMR (125.7 MHz, CDCl3): 0.82, 14.11, 21.56, 22.69, 24.99, 29.15, 29.37, 29.58, 29.67, 29.70, 29.72, 29.73, 31.93, 33.47, 118.67 (q, JC-F = 317.5). 19 F NMR (470.3 MHz, CDCl3): -74.04. HRMS-ESI calcd for C20H43Sn (M - OTf): 403.2381; found: 403.2383. Elemental analysis: calcd for C21H43F3O3SSn: C 45.75; H 7.86; F 10.34; S 5.82; found: C 45.60; H 7.99; F 10.32; S 5.69. Octadecyldimethyltin Trifluoroacetate (7b). Yield 89%, mp 79-81 C. IR (KBr, cm-1): 2953, 2921, 2851, 1678, 1652,

Khobragade et al. 1467, 1453, 1379, 1215, 1201, 1191, 1154, 854, 839, 796, 770, 726, 667, 605, 555, 526, 476. 1H NMR (499.8 MHz, CDCl3): 0.63 (s, 6H), 0.84 (t, J = 7.0 Hz, 3H), 1.20 -1.30 (m, 30H), 1.41 (m, 2H), 1.65 (m, 2H). 13C NMR (125.7 MHz, CDCl3): -2.69, 14.12, 18.52, 22.69, 25.14, 29.08, 29.36, 29.46, 29.60, 29.63, 29.66, 29.69, 31.92, 33.63, 115.04, 161.18. 19F NMR (470.3 MHz, CDCl3): -71.09. 119Sn NMR (186.4 MHz, CDCl3): 191.57. HRMS-EI calcd for C21H40F3O2Sn: 501.2002; found: 501.2001. Elemental analysis: calcd for C22H43F3O2Sn: C 51.28; H 8.41; F 11.06; found: C 51.29; H 8.53; F 10.89. Octadecyldimethyltin Tosylate (7c). Yield 74%, mp 6264 C. IR (KBr, cm-1): 2953, 2919, 2850, 1600, 1497, 1470, 1397, 1378, 1191, 1131, 1044, 1014, 815, 781, 761 719, 695, 568, 542, 521, 496. 1H NMR (499.8 MHz, CDCl3): 0.56 (s, 6H), 0.88 (t, J = 6.8 Hz, 3H), 1.10-1.33 (m, 32H), 1.46 (bm, 2H), 2.38 (s, 3H), 7.19 (m, 2H), 7.55 (m, 2H). 13C NMR (125.7 MHz, CDCl3) 0.77, 14.10, 21.24, 21.39, 22.68, 25.29, 29.31, 29.37, 29.64, 29.68, 29.73, 29.75, 29.76, 29.78, 31.92, 33.67, 125.30, 129.14, 139.09, 142.00. 119Sn NMR (186.4 MHz, CDCl3): 83.08. HRMS-EI calcd for C27H50O3SSn: 574.2503; found: 574.2493. Elemental analysis: calcd for C27H50O3SSn: C 56.55; H 8.79; S 5.59; found: C 56.26; H 8.74; S 5.20.

Acknowledgment. We thank the grant agency of the Czech Republic (203/07/1619) and the U.S. National Science Foundation (OISE 0532040) for financial support. We are grateful to Dr. Zdenk Bastl for comments on the manuscript. e Supporting Information Available: Synthesis and spectral characteristics of silicon-containing compounds. This material is available free of charge via the Internet at http://pubs.acs.org.

H DOI: 10.1021/la101023b

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