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It is, however, difficult to separate the contributions of the cation and of the anion Various methods have yielded the following average values of the primary hydration numbers of the alkali metal cations (the number of methods used is given in brackets and the results are rounded off to the nearest integers): Li+ 5 (5), Na+ 5 (5), K+ 4 (4), Rb + 3 (4), and for the halide ions: F" 4 (3), Cl~ 1 (3), Br" 1 (3), I" 1 (2) The error is 1 water molecule (except for K + , where the error is 2) For divalent ions the values vary between 10 and 14 (according to G Kortiim) For illustration of the variability of the results obtained by various methods, the values obtained for the Na+ ion.

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Figure 13.24. Schematics of the single-molecule operating cycle. Points I IV in (a) represent the four states of an operating cycle. (b) The corresponding force extension plot. Source: Hugel et al., 2002. Reprinted with permission.

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from mobility measurements were 2-4, from the entropy 4, from the compressibility 6-7, from molar volumes 5, from diffusion 1 and from activity coefficients also 1 For the Cl~ ion, these methods yielded the values (in the same order): 4, 3, 0, 1, 0, 0, 1 Of the divalent ions, for example, solution of Mg2+ was measured by the mobility method, yielding a value of 10 to 13, entropy of 13, compressibility of 16 and activity coefficients of 5 (according to B E Conway and J O'M Bockris) Remarkable data on primary hydration shells are obtained in nonaqueous solvents containing a definite amount of water Thus, nitrobenzene saturated with water contains about 02 M H2O Because of much higher dipole moment of water than of nitrobenzene, the ions will be preferentially solvated by water Under these conditions the following values of hydration numbers were obtained: Li+ 6.

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(Z = Wout/Win) is estimated to be 0.1 in this single-molecule device, which is relatively low for optomechanical applications. Other than the SAMs and azobenzene-containing organic polymers, azobenzene-modi ed hybrid polysilsesquioxane gels were also studied for their photomechanical responses. 13.4.2.2. Preparation of Azobenzene-Modi ed Polysilsesquioxane Gels. The BSUA molecules in highly concentrated solid states are very

5, H + 55, Ag+ 44, Na+ 39, K+ 15, Tl + 10, Rb + 08, Cs + 05, tetraethylammonium ion 00, CIO4-O4, NO^ 14 and tetraphenylborate anion 00 (assumption) 124 Ion association As already mentioned, the criterion of complete ionization is the fulfilment of the Kohlrausch and Onsager equations (2415) and (2426) stating that the molar conductivity of the solution has to decrease linearly with the square root of its concentration However, these relationships are valid at moderate concentrations only At high concentrations, distinct deviations are observed which can partly be ascribed to non-bonding electrostatic and other interaction of more complicated nature (cf p 38) and partly to ionic bond formation between ions of opposite charge, ie to ion association (ion-pair formation).

dif cult to isomerize under UV irradiation because of the intermolecular hydrogen-bonding and p p stacking interactions. To avoid these interactions, the BSUA molecules could be diluted in an aerogel network, providing the extra volume (B127 A3) and exible framework needed for the isomerization of the azobenzene ligands. In the aerogel formation process, 15.3 mol% BSUA was diluted with 20.7 mol% bis(triethoxysilyl)ethane (BTE) and 64 mol% TEOS. BTE molecules with CH2CH2 bridges were used to increase the exibility of the gel frameworks. The gel was nally derivitized with hexamethyldisilazine (HMDS) to promote stability and exibility. Thin lms were deposited on the substrates by the casting or spin-coating of the gel dispersed in EtOH. The prepared thin lms exhibited reversible photo and thermal isomerization of azobenzene ligands as detected using UV/visible spectroscopy. As shown in Fig. 13.25, the absorbance of the p p* transition band of the trans isomer at 365 nm decreases under UV irradiation, and the corresponding absorbance of the n p* transition band of the cis isomer at 480 nm increases (Fig. 13.25 curve b), indicating the trans-cis isomerization of azobenzene ligands contained in the lm. Compared with BSUA in EtOH solvent, the n p* transition of the cis isomer in the gel lm exhibits a much higher absorbance, indicating a higher concentration of the cis isomer and a higher molar absorption coef cient (e), which is due to the steric effect. The reverse cis-trans isomerization was achieved when the lm was exposed to room light or heat (Fig. 13.25 curves c,d). The heat treatment at 1001C for 10 min even caused the 365-nm absorption band to exceed that of the asprepared lm, indicating that a certain amount of azobenzene ligands were in the

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The separation of these two effects is indeed rather difficult The species appearing as strong electrolytes in aqueous solutions lose this property in low-permittivity solvents The ion-pair formation converts them to a sort of weak electrolyte In solvents of very low-permittivity (dioxan, benzene) even ion triplets and quadruplets are formed The formation of an ion pair A + + B"^ A + B(1213).

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