zobenzene is a chemical compound composed of two phenyl rings linked by a N=N double bond.

It
is the simplest example of an aryl azo compound. The term 'azobenzene' or simply 'azo' is often
used to refer to a wide class of molecules that share the core azobenzene structure, with different
chemical functional groups extending from the phenyl rings. These azo compounds are considered
as derivatives of diazene (diimide),[1] and are sometimes referred to as 'diazenes'. The diazenes
absorb light strongly and are used as dyes in a variety of industries.
Contents
[hide]

1Synthesis

2Trans-cis isomerization

3Spectroscopic classification

4Photophysics of isomerization

5Photoinduced motions

6Other aspects

7References

Synthesis[edit]
Azobenzene was first described by Eilhard Mitscherlich in 1834.[2][3] Azobenzene was investigated in
1856 byAlfred Nobel as "gelblich-rote krystallinische Blttchen" ("yellowish-red crystalline flakes"
in German).[4] Its original preparation is similar to the modern one. According to the 1858
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.[5]

Trans-cis isomerization[edit]
One of the most intriguing properties of azobenzene (and derivatives) is
the photoisomerization of trans and cisisomers. The two isomers can be switched with particular
wavelengths of light: ultraviolet light, which corresponds to the energy gap of the -* (S2 state)
transition, for trans-to-cis conversion, and blue light, which is equivalent to that of the n-* (S1 state)
transition, for cis-to-trans isomerization. For a variety of reasons, the cis isomer is less stable than
the trans (for instance, it has a distorted configuration and is less delocalized than the trans
configuration). 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.
Thus, cis-azobenzene may thermally relax back, in dark, to the trans isomer. Such thermal relaxation
is slow at room temperature, and competes with photogeneration of the cis-isomer if the compound
is exposed to ultraviolet or visible light.[6]

Spectroscopic classification[edit]
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,[7][8] owing to the subtle differences in their electronic absorption spectra. The
compounds similar to the unsubstituted azobenzene exhibit a low-intensity n-* absorption in the
visible region, and a much higher intensity -* absorption in the ultraviolet. Azos that
are ortho- or para-substituted with electron-donating groups (such asaminos), are classified as
aminoazobenzenes, and tend to closely spaced[7] n-* and -* bands in the visible. The pseudostilbene class is characterized by substituting the 4 and 4' positions of the two azo rings with
electron-donating and electron-withdrawing groups (that is, the two opposite ends of
the aromatic system are functionalized). 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 cisisomers, so that they effectively overlap.[8] 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[edit]
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.
[8]

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, [9] the "concerted
inversion" pathway in which both CNN bond angles bend at the same time.

Photoinduced motions[edit]
The photo-isomerization of azobenzene is a form of light-induced molecular motion. [7][10][11] 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 (trans) 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
(orientational hole burning). Polarized irradiation will make an azo-material anisotropic and therefore
optically birefringent anddichroic. This photo-orientation can also be used to orient other materials
(especially in liquid crystal systems).[12] For instance, it has been used to orient liquid crystal domains
selectively, and to create nonlinear optical (NLO) materials.[13] Azo isomerization can also be used to
photo-switch the liquid crystal phase of a material from cholesteric to nematic[14][15] or to change
the pitch of a cholesteric phase.[16]
In 1995, it was reported that exposing a thin film of azo-polymer to a light intensity (or polarization)
gradient leads to spontaneous surface patterns. In essence, the polymer material will reversibly
deform so as to minimize the amount of material exposed to the light. This phenomenon is not laser
ablation, since it readily occurs at low power and the transformation is reversible. The mechanism of
this surface holography seems related to a new photomechanical effect, involving azobenzene
isomerization.[17]
Bulk expansion and contraction of azobenzene materials have also been observed. In one report, a
thin film was made to bend and unbend by exposing it to polarized light. The direction of the

macroscopic motion could be controlled by the polarization direction. The bending occurred because
the free surface of the material contracted more than the inside of the thin film (due to absorption of
laser light as it passes through the film).

Other aspects[edit]
Azobenzene molecules can be incorporated into polymer matrices as stabilizers. It is also interesting
to note that the rigid rod-like structure of azo molecules allows them to behave as liquidcrystal mesogens in many materials.
The large geometry change associated with azobenzene photoisomerization has also been used to
control protein activity with light. Azobenzene has been attached to ligands (drug) to photo-modulate
their affinity for proteins. Azobenzene has been employed as a photoswitchable tether between a
ligand and the protein: one end of the azobenzene is substituted with a reactive group that attaches
to the target protein. The other end displays a ligand for the protein. Depending on where the
azobenzene is attached, either the cis or trans isomer will present the ligand to the ligand-binding
site, while the other isomer prevents the drug from reaching the site. Again, photoswitching between
isomers turns the protein on and off. When applied to ion channels in the nervous system, this
approach affords optical control of electrical activity in neurons.[18][19]

References[edit]
1.

Jump up^ IUPAC, Compendium of Chemical Terminology, 2nd ed.

(the "Gold Book") (1997). Online corrected version: (2009) "azo
compounds".

2.

Jump up^ Mitscherlich, E. (1834), "Ueber das Stickstoffbenzid". Ann.

Pharm., 12: 311314. doi:10.1002/jlac.18340120282

3.

Jump up^ "Control over molecular motion using the cistrans

photoisomerization of the azo group" Estbaliz Merino and Mara
Ribagorda Beilstein J. Org. Chem.2012, 8, 1071
1090. doi:10.3762/bjoc.8.119

4.

Jump up^ Noble, Alfred (1856). "III. Zur Geschichte des Azobenzols
und des Benzidins". Annalen der Chemie und Pharmacie. 98 (2): 253
256.doi:10.1002/jlac.18560980211.

5.

Jump up^ Bigelow, H. E.; Robinson, D. B.

(1955). "Azobenzene". Org. Synth. 22: 28.;Coll. Vol., 3, p. 103

6.

Jump up^ G. S. Hartley (1937). "The cis form of

Azobenzene". Nature. 140 (3537): 281.doi:10.1038/140281a0.

7.

^ Jump up to:a b c Rau, H. (1990). Rabek, J. F., ed. Photochemistry and

Photophysics. 2. Boca Raton, FL: CRC Press. pp. 119141. ISBN 08493-4042-X.

8.

^ Jump up to:a b c Yager, K. G.; Barrett, C. J. (2008). "Chapter 17 Azobenzene Polymers as Photomechanical and Multifunctional Smart
Materials". In Shahinpoor, M.; Schneider, H.-J. Intelligent Materials.
Cambridge: Royal Society of Chemistry. pp. 426
427. doi:10.1039/9781847558008-00424. ISBN 978-1-84755-800-8.

9.

Jump up^ Diau, E. W.-G. (2004). "A New Trans-to-Cis

Photoisomerization Mechanism of Azobenzene on the S1(n,*)
Surface". The Journal of Physical Chemistry A.108 (6): 950
956. doi:10.1021/jp031149a.

10. Jump up^ Natansohn A.; Rochon, P. (November 2002).

"Photoinduced motions in azo-containing polymers". Chemical
Reviews. 102 (11): 4139
4175.doi:10.1021/cr970155y. PMID 12428986.
11. Jump up^ Yu, Y.; Nakano, M.; Ikeda, T. (2003). "Photomechanics:
Directed bending of a polymer film by light". Nature. 425 (6954):
145. doi:10.1038/425145a.PMID 12968169.
12. Jump up^ Ichimura, K. (2000). "Photoalignment of Liquid-Crystal
Systems". Chemical Reviews. 100 (5): 1847
1874. doi:10.1021/cr980079e. PMID 11777423.
13. Jump up^ Torres-Ziga, V.; Morales-Saavedra, O. G.; Rivera, E.;
Castaeda-Guzmn, R.; Bauelos, J. G.; Ortega-Martnez, R.
(2010). "Preparation and photophysical properties of monomeric
liquid-crystalline azo-dyes embedded in bulk and film SiO 2-sonogel
glasses". Journal of Sol-Gel Science and Technology. 56 (1): 7
18. doi:10.1007/s10971-010-2265-y.
14. Jump up^ Tazuke, S.; Kurihara, S.; Ikeda, T. (1987). "Amplified image
recording in liquid crystal media by means of photochemically
triggered phase transition".Chemistry Letters. 16 (5): 911
914. doi:10.1246/cl.1987.911.
15. Jump up^ Tamaoki, N. (2001). "Cholesteric Liquid Crystals for Color
Information Technology". Advanced Materials. 13 (15): 1135
1147. doi:10.1002/1521-4095(200108)13:15<1135::AIDADMA1135>3.0.CO;2-S.
16. Jump up^ Pieraccini, S.; Masiero, S.; Spada, G. P.; Gottarelli, G.
(2003). "A new axially-chiral photochemical switch". Chemical
Communications. 2003 (5): 598599.doi:10.1039/b211421f.
17. Jump up^ Yager, K. G.; Barrett, C. J. (2006). "Photomechanical
Surface Patterning in Azo-Polymer
Materials". Macromolecules. 39 (26): 9320
9326.doi:10.1021/ma061733s.
18. Jump up^ Gorostiza, P.; Isacoff, E. Y. (October 2008). "Optical
switches for remote and noninvasive control of cell
signaling". Science. 322 (5900): 395
399.doi:10.1126/science.1166022. PMID 18927384.
19. Jump up^ Banghart, M. R.; Volgraf, M.; Trauner, D. (December 2006).
"Engineering light-gated ion channels". Biochemistry. 45 (51): 15129
15141.doi:10.1021/bi0618058. PMID 17176035.

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Aromatic compounds

Azo compounds

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