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These results unambiguously locate the photosensitive azobenzene ligands, along with surfactant, within the uniform nanopores of the self-assembled lms and emphasize the need to accommodate the steric demands of the photoisomerization process by engineering the pore size (as noted previously for adsorbed azobenzene dyes (Ogawa et al, 2000)) and positioning the photoactive species on the pore surfaces Correspondingly, nanocomposite lms prepared using the triblock copolymer surfactant P123, which had larger pores (ca 65 nm in diameter), exhibited a faster and more complete trans-cis isomerization, close to that of TSUA in EtOH solution, presumably because the azobenzene ligands were less sterically constrained It is noteworthy that there exists a difference between the UV/visible spectra of Brij 56 templated nanocomposite lms before (Fig 1312a) and after (Fig 1312b) the surfactant removal.

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3.3.2 Measurement of pH The potentiometric measurement of physicochemical quantities such as dissociation constants, activity coefficients and thus also pH is accompanied by a basic problem, leading to complications that can be solved only if certain assumptions are accepted. Potentiometric measurements in cells without liquid junctions lead to mean activity or mean activity coefficient values (of an electrolyte), rather than the individual ionic values. The EMF of the cell Ag | AgCl(s) | buffer,KCl(m) | H2,Pt (3.3.2) suitable for pH measurements is given by an expression containing the mean activity log aH3O+ = 0A343F/RT(E + - log (mcrycl-) (3.3.3) The pH value obtained in this way is accompanied by an error resulting from the approximation used for the calculation of y c r . Although this error may be small in dilute solutions, the pH values obtained in this manner are not exactly equal to the values corresponding to the absolute definition of

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193 the pH in Eq. (1.4.39). The pH values given by this absolute definition cannot, in principle, be exactly measured. For current practice, the described method of pH measurement is too tedious. Moreover, not hydrogen but glass electrodes are used for routine pH measurements (see Section 6.3). Then the expression for the EMF of the cell consisting of the glass and reference electrodes contains a constant term from Eq. (6.3.10), in addition to the terms present in Eq. (3.3.3); this term must be obtained by calibration. Further, a term describing the liquid junction potential between the reference electrode and the measured solution must also be included. In view of these difficulties an operational definition of pH has been introduced (cf. Section 1.4.6). This definition is based on the concept that the pH is measured with a hydrogen electrode, combined to the measuring galvanic cell with a suitable reference electrode. The reference electrode solution is connected with the solution of the hydrogen electrode through a salt bridge with KC1 of at least 3.5 mol kg"1 concentration. The hydrogen electrode is immersed first into the test solution X with pH(X) and the EMF E(X) is measured, and then into a standard solution S of pH(S), corresponding to potential E(S). It is assumed that the dependence of E on the pH is linear with the Nernst slope, 2.303RT/F. Under these conditions,

For the azobenzene contained in the nanocomposite lm before the surfactant removal, the p p* transition of the trans isomer is at 333 nm and the n p* transition of the cis isomer is at 440 nm After the surfactant removal, the p p* transition of the trans isomer and the n p* transition of the cis isomer are shifted to 350 and 460 nm, respectively In both situations, the absorbance of the n p* transition is quite high, indicating that the molar absorption coef cient (e) of the n p* transition is larger than that in solution owing to the out-of-plane position of the azobenzene phenyl rings This effect may be the result of steric constraint and hydrogen-bonding interactions between the azo- and silanol groups on the silica wall.

(3.3.4)

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In comparison to the azobenzene contained in the nanocomposite lm after the surfactant removal, the appearance of the p p* and the n p* transitions at lower wavelength (blueshift) before the surfactant removal indicates that the azobenzene ligands are out of plane to a larger extent The absorbance at the n p* transition of azobenzene ligands contained in P123-templated lm is lower than that in the Brij 56 templated lm, indicating a less sterically constrained environment because of the larger pore sizes of P123-templated lm The preceding UV/visible data were measured using a re ection mode For TSUA-modi ed nanocomposite thin lms coated on indium tin oxide (ITO)/glass substrates, a transmission mode was adopted to measure the absorbance of the lms In the experiment, the lm was soaked in a Tris buffer solution containing.

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