trans-Azobenzene is planar. The N-N distance is 1.189 Å. cis-Azobenzene is nonplanar with a C-N=N-C dihedral angle of 173.5°. The N-N distance is 1.251 Å. Azobenzene was first described by Eilhard Mitscherlich in 1834. Yellowish-red crystalline flakes of azobenzene were obtained in 1856. Its original preparation is similar to the modern one. According to the 1856 method, nitrobenzene is reduced by iron filings in the presence of acetic acid. In the modern synthesis, zinc is the reductant in the presence of a base. Industrial electrosynthesis using nitrobenzene is also employed. The trans isomer is more stable by approximately 50 kJ/mol, and the barrier to isomerization in the ground state is approximately 100 kJ/mol. . The trans form can be converted to the cis form using a UV wavelength of 300–400 nm. Visible illumination at >400 nm converts the molecule back to the trans form. Alternately, the molecule will thermally relax to the stable trans form.
Reactions
Azobenzene is a weak base, but undergoes protonation at one nitrogen with a pKa = -2.95. It functions as a Lewis base, e.g. toward boron trihalides. It binds to low valence metal centers, e.g. Ni2 is well characterized. It oxidizes to give azoxybenzene. Hydrogenation gives diphenylhydrazine
Trans-cis isomerization
Azobenzene undergo photoisomerization of trans and cis isomers. cis-Azobenzene relaxes back, in dark, to the trans isomer. Such thermal relaxation is slow at room temperature. The two isomers can be switched with particular wavelengths of light: ultraviolet light, which corresponds to the energy gap of the π-π* transition, for trans-to-cis conversion, and blue light, which is equivalent to that of the n-π* transition, for cis-to-trans isomerization. For a variety of reasons, the cis isomer is less stable than the trans. Photoisomerization allows for reversible energy storage.
Spectroscopic classification
The wavelengths at which azobenzene isomerization occurs depends on the particular structure of each azo molecule, but they are typically grouped into three classes: the azobenzene-type molecules, the aminoazobenzenes, and the pseudo-stilbenes. These azos are yellow, orange, and red, respectively, owing to the subtle differences in their electronic absorption spectra. The compounds similar to the unsubstituted azobenzene exhibit a low-intensity n-π* absorption in the visible region, and a much higher intensity π-π* absorption in the ultraviolet. Azos that are ortho- or para-substituted with electron-donating groups, are classified as aminoazobenzenes, and tend to closely spaced n-π* and π-π* bands in the visible. The pseudo-stilbene class is characterized by substituting the 4 and 4' positions of the two azo rings with electron-donating and electron-withdrawing groups. The addition of this push-pull configuration results in a strongly asymmetric electron distribution, which modifies a host of optical properties. In particular, it shifts the absorption spectra of the trans and the cis isomers, so that they effectively overlap. Thus, for these compounds a single wavelength of light in the visible region will induce both the forward and reverse isomerization. Under illumination, these molecules cycle between the two isomeric states.
Photophysics of isomerization
The photo-isomerization of azobenzene is extremely rapid, occurring on picosecond timescales. The rate of the thermal back-relaxation varies greatly depending on the compound: usually hours for azobenzene-type molecules, minutes for aminoazobenzenes, and seconds for the pseudo-stilbenes. The mechanism of isomerization has been the subject of some debate, with two pathways identified as viable: a rotation about the N-N bond, with disruption of the double bond, or via an inversion, with a semi-linear and hybridized transition state. It has been suggested that the trans-to-cis conversion occurs via rotation into the S2 state, whereas inversion gives rise to the cis-to-trans conversion. It is still under discussion which excited state plays a direct role in the series of the photoisomerization behavior. However, the latest research on femtosecond transition spectroscopy has suggested that the S2 state undergoes internal conversion to the S1 state, and then the trans-to-cis isomerization proceeds. Recently another isomerization pathway has been proposed by Diau, the "concerted inversion" pathway in which both CNN bond angles bend at the same time.
Photoinduced motions
The photo-isomerization of azobenzene is a form of light-induced molecular motion. This isomerization can also lead to motion on larger length scales. For instance, polarized light will cause the molecules to isomerize and relax in random positions. However, those relaxed molecules that fall perpendicular to the incoming light polarization will no longer be able to absorb, and will remain fixed. Thus, there is a statistical enrichment of chromophores perpendicular to polarized light. Polarized irradiation will make an azo-material anisotropic and therefore optically birefringent and dichroic. This photo-orientation can also be used to orient other materials.
