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The ring substitution pattern affects both the trans and the cis absorption spectra, and for certain patterns, the absorption spectra of the two isomers overlap signi cantly (notably for the pseudo-stilbenes) In these cases, a single wavelength of light effectuates both the forward and reverse reaction, leading to a mixed stationary state and continual interconversion of the molecules For some interesting azobenzene photomotions, this rapid and ef cient cycling of chromophores is advantageous, whereas in cases where the azo chromophore is used as a switch, it is clearly undesirable The mechanism of isomerization has undergone considerable debate Isomerization takes place either through a rotation about the N N bond, with rupture of the p bond, or through inversion, with a semilinear and hybrizidized transition state, where the p bond remains intact (refer to Fig 14).

The thermal backrelaxation is agreed to be via rotation, whereas for the photochemical isomerization, both mechanisms appear viable (Xie et al, 1993) Historically, the rotation mechanism (as necessarily occurs in stilbene) was favored for photoisomerization, with some early hints that inversion may be contributing (Gegiou et al, 1968) More recent experiments, based on matrix or molecular constraints to the azobenzene isomerization, strongly support inversion (Altomare et al, 1997; Liu et al, 1992; Naito et al, 1991; Rau and Lueddecke, 1982) Studies using picosecond Raman and femtosecond uorescence show a double bond (N=N) in the excited state, con rming the inversion mechanism (Fujino et al, 2001; Fujino.

The key here is wp_add_dashboard_widget(), to which you pass first an identifying ID of the widget (which is 'dashboard_reminder_widget' in this case), and then the text label that should describe the widget, and finally the name of the function containing the Dashboard

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Figure 1.4. The mechanism of azobenzene isomerization proceeds either via rotation or inversion. The cis state has the phenyl rings tilted at 901 with respect to the CNNC plane.

and Tahara, 2000). In contrast, Ho et al. (2001) found evidence that the pathway is compound-speci c: a nitro-substituted azobenzene photoisomerized via the rotation pathway. Furthermore, ab initio and density functional theory calculations indicate that both pathways are energetically accessible, although inversion is preferred (Angeli et al., 1996; Jursic, 1996). Thus, both mechanisms may be competing, with a different one dominating depending on the particular chromophore and environment. The emerging consensus nevertheless appears to be that inversion is the dominant pathway for most azobenzenes (Ikeda and Tsutsumi, 1995). The availability of the inversion mechanism explains how azos are able to isomerize easily even in rigid matrices, such as glassy polymers, since the inversion mechanism has a much smaller free volume requirement than rotation. The thermal back-relaxation is generally rst order, although a glassy polymer matrix can lead to anomalously fast decay components (Barrett et al., 1995, 1994; Paik and Morawetz, 1972; Priest and Sifain, 1971), attributed to a distribution of chromophores in highly strained con gurations. Higher matrix crystallinity increases the rate of decay (Sarkar et al., 2001). The decay rate can act as a probe of local environment and molecular conformation (Tanaka et al., 2004; Norman and Barrett, 2002). The back-relaxation of azobenzene is acid catalyzed (Rau et al., 1981), although strongly acidic conditions will lead to side reactions (Hartley, 1938). For the parent azobenzene molecule, quantum yields (which can be indirectly measured spectroscopically (Shen and Rau, 1991; Priest and Sifain, 1971; Malkin and Fischer, 1962) are on the order of 0.6 for the trans-cis

widget s content (obviously the dashboard_reminder() function).Worth knowing is that the Dashboard widget ID, which is the first parameter passed to wp_add_dashboard_widget(), is also the class the widget will get should you want some fancy CSS stylings. Pause for a moment and look at the wp_add_dashboard_widget() function. The first parameter is the widget ID, the second the widget name that you want to display, and then there s the callback of the function containing the actual widget content. There s a fourth parameter as well, called $control_callback, and it passes a null value by default, and is optional. You can use that to give your widget settings by passing a function containing whatever settings you want to let the user fiddle with. None for this example, but it may be a good idea to keep in mind that you can pass a fourth parameter for more functionality in your Dashboard widget. Returning to the example, you need to add the widget action to the wp_dashboard_setup hook, using add_action():

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