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Now the origin of the scale must be defined, i.e. a pH value must be selected for a standard (as close as possible to the value expected on the basis of definition 1.4.46). A solution of potassium hydrogen phthalate with a molality of 0.05 mol-kg" 1 has been selected as the reference value pH standard (RVS). The pH of the saturated solution of potassium hydrogen phthalate containing chloride molarity m cl - is given by the equation p H = -0.4343F( + Ag/AgC1) + log [m c l -y c r ] (3.3.5) where E is the EMF of the cell (3.3.2). The first two terms on the right-hand side can be measured. If the pH of the cell (3.3.2) is determined for various values of m c r and if the sum of these two terms if plotted vs m cl -, a nearly linear dependence is obtained which may easily be extrapolated to zero concentration of chloride ions. For the pH(RVS), the pH of the standard phthalate solution alone, we have then pH(RVS) = - lim [0.4343F(E + E Ag/AgC1 )/ J Rr-logm C i-]+ lim log yc, .

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Adding substituents to the azobenzene rings may lead to minor or major changes in spectroscopic character Of particular interest is ortho- or parasubstitution with an electron-donating group (usually an amino, NH2), which results in a new class of compounds In these aminoazobenzenes, the n-p* and p-p* bands are much closer In fact, the n-p* may be completely buried beneath the intense p-p* Although azobenzenes are fairly insensitive to solvent polarity, aminoazobenzene absorption bands shift to higher energy in nonpolar solvents and shift to lower energy in polar solvents Substituting azobenzene at the 4 and 4u positions with an electron-donor and an electron-acceptor (such as an amino and a nitro, NO2, group) leads to a strongly asymmetric electron distribution (often referred to as a push pull substitution pattern) This shifts the p-p* absorption to lower energy, toward the red and past the n-p*.

Yes (Hitachi Embedded [Only for VT-i])

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(3.3.6) The value of lim log y cl - may not be put equal to zero, as the overall ionic strength of the solution is not equal to zero, but it may be calculated using the Bates-Guggenheim equation (1.3.35). The values of pH(RVS) obtained in this way are listed in Table 3.7.

This reversed ordering of the absorption bands de nes the third spectroscopic class, the pseudo-stilbenes (in analogy to stilbene, phenyl C=C phenyl) The pseudo-stilbenes are very sensitive to local environment, which can be useful in some applications Especially in condensed phases, the azos are also sensitive to packing and aggregation The p p stacking gives rise to shifts of the absorption spectrum If the azo dipoles have a parallel (head-to-head) alignment, they are called J-aggregates, and give rise to a redshift of the spectrum (bathochromic) as compared with the isolated chromophore If the dipoles are antiparallel (head-to-tail), they are called H-aggregates and lead to a blueshift (hypsochromic) Fluorescence is seen in some aminoazobenzenes and many pseudo-stilbenes but not in azobenzenes, whereas phosphorescence is absent in all the three classes.

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194 Table 3.7 Values of pH(RVS) for the reference value standard of 0.05 mol kg"1 potassium hydrogen phthalate at various temperatures

GbE NIC PCI-Express (4 Lane)

By altering the electron density, the substitution pattern necessarily affects the dipole moment, and in fact all the higher order multipole moments This becomes signi cant in many nonlinear optical (NLO) studies For instance, the chromophore s dipole moment can be used to orient with an applied electric eld (poling), and the higher order moments of course de ne the molecule s nonlinear response (Delaire and Nakatani, 2000) In particular, the strongly asymmetric distribution of the delocalized electrons that results from push pull substitution results in an excellent NLO chromophore..

0 5 10 15 20 25 30

pH(RVS) 4.000 3.998 3.997 3.998 4.001 4.005 4.011

Key to some of the most intriguing results and interesting applications of azobenzenes is the facile and reversible photoisomerization about the azo bond, converting between the trans (E ) and cis (Z) geometric isomers (Fig. 1.3). This photoisomerization is completely reversible and free from side reactions, prompting Rau to characterize it as one of the cleanest photoreactions known. (Rau, 1990) The trans isomer is more stable by B50 kJ mol 1 (Mita et al., 1989; Schulze et al., 1977), and the energy barrier to the photoexcited state (barrier to isomerization) is on the order of 200 kJ mol 1 (Monti et al., 1982). Thus, in the dark, most azobenzene molecules will be found in the trans form. On absorption of a photon (with a wavelength in the trans absorption band), the azobenzene will convert, with high ef ciency, into the cis isomer. A second wavelength of light (corresponding to the cis absorption band) can cause the back-conversion.

2 Sockets (4way)

C 35 37 40 45 50 55 60

trans cis ~50 kJ mol 1 cis (Z )

Yes (Intel VT-x)

pH(RVS) 4.018 4.022 4.027 4.038 4.050 4.064 4.080

N N trans (E )

C 65 70 75 80 85 90 95

GbE NIC PCI-Express (4 Lane)

trans (E ) (a)

pH(RVS) 4.097 4.116 4.137 4.159 4.183 4.210 4.240

cis (Z ) (b)

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