Azo compound

Azo compounds are compounds bearing the functional group R-N=N-R', in which R and R' can be either aryl or alkyl. IU !" defines a#o compounds as$ %&eri'ati'es of dia#ene (diimide), *N=N*, wherein both hydrogens are substituted by hydrocarbyl groups, e.g. hN=N h a#oben#ene or diphenyldia#ene.%+,- .he more stable deri'ati'es contain two aryl groups. .he N=N group is called an azo group. .he name a#o comes from azote, the /rench name for nitrogen that is deri'ed from the 0reek a (not) 1 zoe (to li'e).

As dyes and pigments

2ellow a#o dye !s a conse3uence of 4-delocali#ation, aryl a#o compounds ha'e 'i'id colors, especially reds, oranges, and yellows. .herefore, they are used as dyes, and are commonly known as azo dyes, an e5ample of which is &isperse 6range ,. 7ome a#o compounds, eg. methyl orange, are used as acid-base indicators due to the different colors of their acid and salt forms. .he de'elopment of a#o dyes was an important step in the de'elopment of the chemical industry. !#o pigments are colorless particles (typically earths or clays), which ha'e been colored using an a#o compound. !#o pigments are important in a 'ariety of paints including artist's paints. .hey ha'e e5cellent coloring properties, again mainly in the yellow to red range, as well as lightfastness. .he lightfastness depends not only on the properties of the organic a#o compound, but also on the way they ha'e been adsorbed on the pigment carrier. 8any a#o pigments are non-to5ic, although some, such as dinitroaniline orange, orthonitroaniline orange, or pigment orange ,, 9, and : ha'e been found to be mutagenic. +9;ikewise, se'eral case studies ha'e linked a#o pigments with <asal "ell "arcinoma.+=-

Organic chemistry
Aryl azo compounds
!ryl a#o compounds are usually stable, crystalline species. !#oben#ene is the prototypical aromatic a#o compound. It e5ists mainly as the trans isomer, but upon photolysis, con'erts to the cis isomer. !romatic a#o compounds can be synthesi#ed by using an a#o coupling reaction, which entails an electrophilic substitution reaction where an aryl dia#onium cation attacks another aryl ring, especially those substituted with electron-releasing groups.+>- 7ince dia#onium salts are often unstable near room temperature, the a#o coupling reactions are typically conducted near ice temperatures. .he o5idation of hydra#ines (R-N*-N*-R') also gi'es a#o compounds.+:- !#o dyes deri'ed from ben#idine are carcinogens? e5posure to them has classically been associated with bladder cancer.+@- !ccordingly, the production of ben#idine a#o dyes was discontinued in the ,ABCs %in the most important western industriali#ed countries%.+D-

Alkyl azo compounds

!liphatic a#o compounds (R andEor R' = aliphatic) are less commonly encountered than the aryl a#o compounds. 6ne e5ample is diethyldia#ene, FtN=NFt. +B- !t ele'ated temperatures or upon irradiation, the carbon-nitrogen ("-N) bonds in certain alkyl a#o compounds clea'e with the loss of nitrogen gas to generate radicals. 6wing to this process, some aliphatic a#o compounds are utili#ed as radical initiators. Representati'e is !#obisisobutylonitrile (!I<N) which is widely used as an initiator in polymeri#ation. <ecause of their instability, especially for aliphatic ones, care should be taken with the handling of a#o compounds or an e5plosion may occur.

Azo coupling
!n azo coupling is an organic reaction between a dia#onium compound and a dialkylaniline ("@*:NR9), phenol or other aromatic compound which produces an a#o compound +,- +9- . In this reaction the dia#onium salt is an electrophile and the acti'ated arene is a nucleophile in an electrophilic aromatic substitution. In most cases, including the e5ample below, the dia#onium compound is also aromatic. .he product will absorb longer wa'elengths of light than the reactants because of increased conGugation. !romatic a#o compounds tend to be brightly colored due to the e5tended conGugated systems? many are used as dyes. !#o couplings are important in the production of dyes and p* indicators such as methyl red and pigment red ,DC. rontosil and other sulfa drugs are also produced using this reaction. !n e5ample is the synthesis of the dye organol brown from aniline and ,-naphthol$

Azobenzene
!#oben#ene photoisomeri#ation. .he trans form (left) can be con'erted to the cis form (right) using an appropriate wa'elength of light. ! different wa'elength of light can be used to con'ert the molecule back to the trans form. !lternately, the molecule will thermally rela5 to the stable trans form. Azobenzene is a chemical compound composed of two phenyl rings linked by a N=N double bond. It is the best known e5ample of an a#o compound. .he term 'a#oben#ene' or simply 'a#o' is often used to refer to a wide class of molecules that share the core a#oben#ene structure, with different chemical functional groups e5tending from the phenyl rings. .hese a#o compounds are considered as deri'ati'es of dia#ene (diimideH,+,and are sometimes referred to as 'dia#enes'. .he dia#enes strongly absorb light and are used as dyes in a 'ariety of industries.

Synthesis

!#oben#ene was first described in ,B:@ as %gelblich-rote krystallinische <lIttchen% (%yellowish-red crystalline flakes% in 0erman).+9- Its original preparation is similar to the modern one. !ccording to the ,B:B method, nitroben#ene is reduced by iron filings in the presence of acetic acid. In the modern synthesis, #inc is the reductant in the presence of a base.+=-

Trans-cis isomerization
6ne of the most intriguing properties of a#oben#ene (and deri'ati'es) is the photoisomeri#ation of trans and cis isomers. .he two isomers can be switched with particular wa'elengths of light$ ultra'iolet light, which corresponds to the energy gap of the J-JK (S2 state) transition, for trans-to-cis con'ersion, and blue light, which is e3ui'alent to that of the n-JK (S1 state) transition, for cis-to-trans isomeri#ation. /or a 'ariety of reasons, the cis isomer is less stable than the trans (for instance, it has a distorted configuration and is less delocali#ed than the trans configuration). .hus, cisa#oben#ene will thermally rela5 back to the trans 'ia cis-to-trans isomeri#ation. .he trans isomer is more stable by appro5imately :C kLEmol, and the barrier to photo-isomeri#ation is appro5imately 9CC kLEmol.

Spectroscopic classification
.he wa'elengths at which a#oben#ene isomeri#ation occurs depends on the particular structure of each a#o molecule, but they are typically grouped into three classes$ the a#oben#ene-type molecules, the aminoa#oben#enes, and the pseudo-stilbenes. .hese a#os are yellow, orange, and red, respecti'ely, owing to the subtle differences in their electronic absorption spectra. .he compounds similar to the unsubstituted a#oben#ene e5hibit a low-intensity n-JK absorption in the 'isible region, and a much higher intensity J-JK absorption in the ultra'iolet. !#os that are ortho- or para-substituted with electrondonating groups (such as aminos), are classified as aminoa#oben#enes, and tend to closely spaced n-JK and J-JK bands in the 'isible. .he pseudo-stilbene class is characteri#ed by substituting the > and >' positions of the two a#o rings with electrondonating and electron-withdrawing groups (that is, the two opposite ends of the aromatic system are functionali#ed). .he 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 effecti'ely o'erlap. .hus, for these compounds a single wa'elength of light in the 'isible region will induce both the forward and re'erse isomeri#ation. Under illumination, these molecules cycle between the two isomeric states.

Photophysics of isomerization
.he photo-isomeri#ation of a#oben#ene is e5tremely rapid, occurring on picosecond timescales. .he rate of the thermal back-rela5ation 'aries greatly depending on the compound$ usually hours for a#oben#ene-type molecules, minutes for aminoa#oben#enes, and seconds for the pseudo-stilbenes.

.he mechanism of isomeri#ation has been the subGect of some debate, with two pathways identified as 'iable$ a rotation about the N-N bond, with disruption of the double bond, or 'ia an inversion, with a semi-linear and hybridi#ed transition state. It has been suggested that the trans-to-cis con'ersion occurs 'ia rotation into the S2 state, whereas in'ersion gi'es rise to the cis-to-trans con'ersion. It is still under discussion which e5cited state plays a direct role in the series of the photoisomeri#ation beha'ior. *owe'er, the latest research on femtosecond transition spectroscopy has suggested that the S2 state undergoes internal con'ersion to the S1 state, and then the trans-to-cis isomeri#ation proceeds. Recently another isomeri#ation pathway has been proposed by &iau , the %concerted in'ersion% pathway in which both "NN bond angles bend at the same time.

Photoinduced motions
.he photo-isomeri#ation of a#oben#ene is a form of light-induced molecular motion . .his isomeri#ation can also lead to motion on larger length scales. /or instance, polari#ed light will cause the molecules to isomeri#e and rela5 in random positions. *owe'er, those rela5ed (trans) molecules that fall perpendicular to the incoming light polari#ation will no longer be able to absorb, and will remain fi5ed. .hus, there is a statistical enrichment of chromophores perpendicular to polari#ed light (orientational hole burning). olari#ed irradiation will make an a#o-material anisotropic and therefore optically birefringent and dichroic. .his photo-orientation can also be used to orient other materials (especially in li3uid crystal systems)+B-. /or instance, it has been used to selecti'ely orient li3uid crystal domains, and used to create nonlinear optical (N;6) materials. !#o isomeri#ation can also be used to photo-switch the li3uid crystal phase of a material from cholesteric to nematic+A-+,C- or to change the pitch of a cholesteric phase.+,,In ,AA:, it was reported that e5posing a thin film of a#o-polymer to a light intensity (or polari#ation) gradient leads to spontaneous surface patterns. In essence, the polymer material will re'ersibly deform so as to minimi#e the amount of material e5posed to the light. .his phenomenon is not laser ablation, since it readily occurs at low power and the transformation is re'ersible. .his detailed mechanism of this surface holography is still unresol'ed, although it is clearly related to the a#oben#ene isomeri#ation. <ulk e5pansion and contraction of a#oben#ene materials ha'e also been obser'ed. In one report, a thin film was made to bend and unbend by e5posing it to polari#ed light. .he direction of the macroscopic motion could be controlled by the polari#ation direction. .he 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
!#oben#ene molecules can be incorporated into polymer matrices as stabili#ers. It is also interesting to note that the rigid rod-like structure of a#o molecules allows them to beha'e as li3uid-crystal mesogens in many materials.

.he large geometry change associated with a#oben#ene photoisomeri#ation has also been used to control protein acti'ity with light. !#oben#ene has been attached to ligands (drug) to photo-modulate their affinity for proteins. !#oben#ene has been employed as a photoswitchable tether between a ligand and the protein$ one end of the a#oben#ene is substituted with a reacti'e group that attaches to the target protein. .he other end displays a ligand for the protein. &epending on the where the a#oben#ene is attached, either the cis or trans isomer will present the ligand to the ligand-binding site, while the other isomer pre'ents the drug from reaching the site. !gain, photoswitching between isomers turns the protein on and off. Mhen applied to ion channels in the ner'ous system, this approach affords optical control of electrical acti'ity in neurons.