Calix[6]arene-based rotaxanes and pseudorotaxanes on Si(100) surface

treatment of the plate with the NMPI solution finally determines a large enhancement of the N+ peak that is almost as large as the one of NH (NH/N+ = 2.1). In principle, this ratio is in perfect agreement with a 1:1 complexation between the cavity of 21 and NMPI. However, the corresponding N+/I ratio should be 1, instead of the calculated 6.6. This could mean that: a) the NH/N+ ratio is fortuitously 2 or more reasonably that b) the iodine present on the surface has been partially exchanged with other anions not evaluated (oxygenated anions are not visible by XPS). Further studies must be accomplished to totally disclose the effictiveness of these binding processes, even though this study represents a good starting point.

reactions required for the introduction of the phenylurea groups on the upper rim of the macrocycle. The introduction of these insaturations on the alkyl chains of the viologen axle certainly requires less synthetic efforts and this strategy was thus adopted.

Synthesis of the viologen-based axle

We chosen to synthesize axle 24 that is characterized by redox-active bypridinium core alkylated with a pentyl and 10-undecenyl chains according to synthetic pathway described in scheme 4.3. Initially 4,4’-bipyridyl was refluxed in acetonitrile for 72h in the presence of a stoichiometric defect of 1-pentyl tosylate to afford the tosylate salt 23 in high yields.

Successively, the viologen salt 24 was obtained in high yields by heating a solution of 23 in acetonitrile in the presence of an excess of undec-10-enyl 4-methylbenzenesulfonate (see experimental).

Scheme 4.3 Synthesis of the viologen based axle 24.

Figure 4.10 ¹H NMR spectra in 300MHz in DMSO-d6 of axle 24.

In the ¹H NMR spectrum of 24 in DMSO-d₆ (see figure 4.10) it is possible to observe the

ppm, respectively, corresponding to the two tosylate anions, and two doublets at δ = 9.38 and 8.77 ppm relative to the aromatic protons of the 4,4’-bipyridyl unit. The signals of the two CH₂ groups directly linked to the nitrogen atons are not distinguishable and visible as a unique triplet at δ = 4.67 ppm. The remnants CH₂ groups of the two alkyl chains give rise to a typical pattern of aliphatic signals of long alkyl chains. The ω-insaturation generates a typical pattern of multiplet signals at δ = 5.8-5.7 and 5.0-4.8 ppm

Functionalization of the Si(100) surface

The insertion of the pseudorotaxane system on the silicon surface was carried out using a simple strategy: a) dip coating of a silicon plate in a toluene solution containing equimolar amounts of axle 24 and triphenylureido-calix[6]arene 25; b) irradiation of the system; c) extensive rinsing of the irradiated silicon plate with low polar solvents in order to remove all the material not covalently attached on the surface. Calix[6]arene 25 (see Figure 4.11) was chosen as the “wheel” because it has been extensively verified that 25 gives rise to the formation of stable pseudorotaxanes in apolar solvents (logK > 6) with axles similar to 24.¹¹

Figure 4.11 Synthesis of two isomers of the pseudorotaxane 25 ⊃ 24 and its anchoring on Si(100) surface

As described in 2.1.6, the lacking of control elements (stoppers) in the axle 24 generates the formation of a mixture of two pseudorotaxane isomers because the threading process can occur indifferently from both rims of the macrocycle. The two isomers (up and down, figure 4.11) differ for the relative position of the asymmetric axle 24 inside the asymmetric aromatic cavity of 25 which bears on its rims different substituents (see Figure 4.11).

XPS and electrochemical studies of the functionalized Si(100) surface.

The results of the XPS analysis carried out on the functionalized silicon surface were summarized in table 4.2 and in figure 4.12.

Figure 4.12 XPS spectral regions for 24@Si: a) Si 2p and b) N 1s. XPS spectral region for 25⊃24@Si: c) Si 2p and d) N 1s. e) Cyclic voltammetric curve of 25⊃24@Si surface (scan rate, 200 mV/s, Ag/Ag⁺ electrode used as reference) and f) N 1s XPS spectral region of the 25⊃24@Si surface after the voltammetric cycle. Binding energy in figures are not referenced to BE of C 1s.

For comparison also a Si plate functionalized with axle 24 was analysed. The XPS spectral region relative to Si 2p shows that, after functionalization, the Si(100) surface does not present a relevant amount of oxidized silicon. (See Figures 4.12a and 4.12c, BE in figure are not referenced to the signal of C 1s of calixarene). The analysis of the N 1s region offers more interesting results: the surface functionalized with 24 (24@Si) gives rise to a unique

4.12b),¹³ while the surface covered with the pseudorotaxanes (25⊃24@Si) presents two signals which were assigned to the NH of the urea groups (lower BE) and to the N+ of the bypyridinium unit (higher BE) (see Figure 4.12d).

Table 4.2 Theoretical and experimental elemental ratios of Si(100) surfaces functionalized with axle (24@Si) and with the mixture of pseudorotaxanes (25⊃24@Si) as determined by XPS spectroscopy (error ± 10%)

Entry Designation C/N (theor) C/N (exp) NH/N+ (theor) NH/N+ (exp)

1 24@Si 20 22 - -

2 25⊃24@Si 14.5 16.2 3 1

3 25⊃24@Si after reduction 20 14.9 - 0.3

The NH/N+ elemental ratio of ∼1 (see table 4.2, entry 2) determined for 25⊃24@Si evidences that this surface is still covered with a considerable amount of uncomplexed axle 24 since the expected ratio should be 3. This result could imply that: a) the anchoring reaction is faster than the threading process occurring in solution between the calixarene 25 and 24, b) during the irradiation process the temperature of the toluene solution containing the pseudorotaxanes increases up to ∼50 °C.

In a previous study we have demonstrated the possibility to electrochemically switch the threading-dethreading process of viologen-calix[6]arene based pseudorotaxane systems in solution of CH₂Cl₂.^11b In particular, this study was conducted using cyclic voltammetry (see Figure 4.13) and revealed that the free axle (Figure 4.13a) shows two monoelectronic and reversible reduction processes (E_1/2 = -0.29 V, E_1/2 = -0.81 V vs SCE) characteristic of the viologen unit; the complexed axle shows instead a shift of the first reduction potential to more negative values, while the second potential remains equal to the one of the free axle. This confirmed that axle dethreading occurs after the first reduction event.

13. The experimental values of the BE of the N 1s signal were corrected as usual taking into account the value of the carbon taken as reference. The corrected values are in agreement with the reported literature data relative to charged N 1s species, see: (a) S.M. Mendoza, J. Berná, E.M. Pérez, E.R. Kay, A. Mateo-Alonso, C. De Nadaï, S. Zhang, J. Baggerman, P.G. Wiering, D.A. Leigh, M. Prato, A.M. Brouwer, P. Rudolf, J.

Electron .Spectrosc., 2008, 165, 42; (b) S. M. Mendoza, C. M. Whelan, J. P. Jalkanen, F. Zerbetto, F. G.

Gatti, E. R. Kay, D. A. Leigh, M. Lubomska, P. Rudolf, J. Chem. Phys., 2005, 123, 244708, (c) H. Suga, E.

Koyama, H. Tokuhisa, K. Fujiwara, Y. Nagawa, T. Nakamura, Y. Nishioka, M. Kanesato, W. Mizutani, T.

Ishida, Surf. Sci., 2007, 601, 68.

Figure 4.13 Cyclic voltammetric curves for the first and second reduction of the viologen unit in a) dioctyl violgen and in b) the pseudorotaxane formed between a trioctyltriphenylureido calix[6]arene and dioctyl viologen (TBAPF6, 293 K; scan rate 0.2V/s, CH2Cl2).

Starting from these interesting results we did few attempts to study the threading-dethreading process of the 25⊃24@Si surface using cyclic voltammetry techniques. This study was carried out to demonstrate the feasibility and reseversibily of the threading process also at the solid-liquid interface. However, differently from the studies in solution, this electrochemical experiment requires the use of the functionalized silicon surface (plate) as one of the electrodes and the current involved in the processes at the interface are sensibily lower than those recorded in homogeneous solution.

The cyclic voltammogram reported in Figure 4.12e is characterized by a very low signal to noise ratio that prevents the identification of possible reduction potentials of the viologen unit. Despite this disappointing result, we analyzed through XPS spectroscopy the silicon plate after the reduction cycle experiment (see Figure 4.12f). The N 1s spectral region evidences a clear decrease of the peak corresponding to the NH species. Indeed, NH/N⁺ quantitative ratio decreases from 1 to 0.3 (see Table 4.2). The N 1s region of the XPS spectrum shows, after deconvolution, also the presence of a weak signal at lower BE. Even though the nature of this peak has not been assigned yet, it is reasonable to assume it originates from reduced nitrogen species deriving from either the reduced axle or reduced wheel. All the results obtained in this work are preliminary and more studies are in progress to disclose and improve these kind of systems.