We have used infrared spectroscopy, ellipsometry, and contact angle measurements to study self-assembled monolayer (SAM) formation on aluminum native oxide from three alkanephosphonic acids:  CF3(CF2)7(CH2)11PO3H2 (F8H11PA), and CH3(CH2) n PO3H2 (n = 15 (H16PA); n = 21 (H22PA)). These compounds show significant differences in film structure and film formation kinetics. Strikingly, the methylene segment of the semifluorinated F8H11PA SAM never reaches an ordered state even at long assembly times. This contrasts with the ordered chains in equilibrium films from H16PA and H22PA. We attribute this behavior to steric effects of the fluorocarbon segment and the phosphonic acid headgroup. F8H11PA represents an amphiphile in which bulky head and tail groups prevent an interposed hydrocarbon segment from ordering. For all three phosphonic acids, negative peaks attributed to loss of Al−OH groups in the infrared spectra of the monolayers are consistent with a condensation reaction between the acids and surface hydroxyls to form bound aluminophosphonate salts. With respect to kinetics, our results indicate that F8H11PA approaches its equilibrium film structure considerably faster than the hydrocarbon phosphonic acids. We interpret the structural dependence of film formation kinetics in terms of the T c formalism advanced by Rondelez and co-workers (Langmuir 1994, 10, 4367−4373). We also suggest that the accelerated film formation exhibited by F8H11PA may be due to chain entanglement and solubility effects, to the extent that this species may self-assemble as islands of approximately vertically oriented chains which fill in as coverage increases. H22PA may also deposit as islands, but in contrast, film formation for H16PA probably involves initially disordered chains with higher tilt angles that order and reorient as film assembly proceeds.

equation,26 and HSAB theory20 have all been used in attempts to correlate reactivity with structural or thermodynamic properties. Success of these correlations is rather limited, as absolute and even relative rates of SN2 reactions have been found to be highly solvent (2) (a) Swain, C.

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Dynamic contact angle studies on self-assembled thin films from C 7 F 15 CH 2 OCH 2 CH 2 CH 2 SiCl 3 reveal a range of interesting behavior. Solution-based processing conditions have been identified that allow preparation of essentially monolayer films on quartz exhibiting water adv/rec contact angles of 119/104 ( 2°and extremely low contact angle hysteresis (hexadecane adv/rec ) 74/70°, heptane adv/rec ) 56/55°) with hydrocarbon liquids. This compound provides an example of a fluorinated trichlorosilane that is able to deliver lowhysteresis films by deposition at room temperature. Adsorption of silane oligomers, formed by hydrolysis and condensation reactions in solution, was also found to occur, slower than but competitive with monolayer formation. This process became more significant as dip coating times increased. Ellipsometric data on silicon wafers confirmed that film thicknesses increased with dip time, while AFM imaging showed that the oligomeric material was deposited in the form of particulates. The effects of this process on water dynamic contact angles are discussed. We also compare contact angles on these films with those on films prepared from C n F 2n+1 CH 2 CH 2 SiCl 3 (n ) 6, 8, 10) and draw some conclusions regarding structure-property effects in these systems. Finally, we propose a mechanism that can account qualitatively for the bulk of the results observed here. Its central feature is reaction of the fluorinated alkyltrichlorosilane with surface-adsorbed water to yield a self-assembled monolayer consisting of silanetriol molecules hydrogen-bonded to the substrate. Effects of high humidity aging on dynamic contact angles of these films suggest that they are at most only lightly cross-linked when prepared under conditions utilized here.

Imidazolium functionality has played a prominent role in research on anion exchange membranes for use in alkaline electrochemical devices. Base stability and degradation of these materials has been much studied, but in many instances, product pathways have not been thoroughly delineated. We report an NMR study of base-induced decomposition products from three benzylimidazolium salts bearing varying extents of methyl substitution on the imidazolium ring. The major products are consistent with a hydrolytic ring fragmentation pathway as the principal mode of decomposition. We observe several new products not previously reported in the literature on imidazolium salt degradation, including benzilic acid rearrangement products formally derived from intermediate 1,2-dicarbonyl compounds or their equivalents. However, the overall reactions are complex, the yields of observed products do not account for all consumed starting materials, and mechanistic ambiguities remain.

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Although unimolecular reactions of gas-phase ions are important and are commonly observed, it is difficult to gain much mechanistic insight into how highly activated ions decompose.1•2 We wish to report a detailed mechanistic study utilizing infrared multiphoton (IRMP) photochemistry3 in an ion cyclotron resonance (ICR) spectrometer.4 The mechanism of the IRMP-induced loss of methane from teri-butoxide ion to yield acetone enolate ion was probed by competitive kinetic isotope effects. The observation of unusually large secondary isotope effects (up to 6.9) and a small primary effect (1.6-2.0) is indicative of a stepwise mechanism involving bond cleavage as the first step and a subsequent hydrogen-transfer reaction from an intermediate ionmolecule complex.5