In chemistry, photoisomerization is a form of isomerization induced by photoexcitation. [2] Both reversible and irreversible photoisomerizations are known for photoswitchable compounds. The term "photoisomerization" usually, however, refers to a reversible process.
Photoisomerization of the compound retinal in the eye allows for vision.
Photoisomerizable substrates have been put to practical use, for instance, in pigments for rewritable CDs, DVDs, and 3D optical data storage solutions. In addition, interest in photoisomerizable molecules has been aimed at molecular devices, such as molecular switches, [3] [4] molecular motors, [5] and molecular electronics.
Another class of device that uses the photoisomerization process is as an additive in liquid crystals to change their linear and nonlinear properties. [6] Due to the photoisomerization is possible to induce a molecular reorientation in the liquid crystal bulk, which is used in holography, [7] as spatial filter [8] or optical switching. [9]
Azobenzenes, [1] stilbenes, [10] spiropyrans, [11] are prominent classes of compounds subject to photoisomerism.
In the presence of a catalyst, norbornadiene converts to quadricyclane via ~300nm UV radiation . When converted back to norbornadiene, quadryicyclane’s ring strain energy is liberated in the form of heat (ΔH = −89 kJ/mol). This reaction has been proposed to store solar energy (photoswitchs). [12]
Photoisomerization behavior can be roughly categorized into several classes. Two major classes are trans–cis (or E–Z) conversion, and open-closed ring transition. Examples of the former include stilbene and azobenzene. This type of compounds has a double bond, and rotation or inversion around the double bond affords isomerization between the two states. [13] Examples of the latter include fulgide and diarylethene. This type of compounds undergoes bond cleavage and bond creation upon irradiation with particular wavelengths of light. Still another class is the di-π-methane rearrangement.
Many complexes are often photosensitive and many of these complexes undergo photoisomerization. [14] One case is the conversion of the colorless cis-bis(triphenylphosphine)platinum chloride to the yellow trans isomer.
Some coordination complexes undergo change in their spin state upon illumination, i.e. these are photosensitive spin crossover complexes. [15]
![Light-induced spin-crossover of [Fe(pyCH2NH2)3] , which switches from high and low-spin Fe(picNH2)3.png](http://upload.wikimedia.org/wikipedia/commons/thumb/6/6a/Fe%28picNH2%293.png/220px-Fe%28picNH2%293.png)
Photochemistry is the branch of chemistry concerned with the chemical effects of light. Generally, this term is used to describe a chemical reaction caused by absorption of ultraviolet, visible light (400–750 nm) or infrared radiation (750–2500 nm).
Azobenzene is a photoswitchable 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 similar compounds. These azo compounds are considered as derivatives of diazene (diimide), and are sometimes referred to as 'diazenes'. The diazenes absorb light strongly and are common dyes.
Diarylethene is the general name of a class of chemical compounds that have aromatic functional groups bonded to each end of a carbon–carbon double bond. The simplest example is stilbene, which has two geometric isomers, E and Z.
Molecular machines are a class of molecules typically described as an assembly of a discrete number of molecular components intended to produce mechanical movements in response to specific stimuli, mimicking macromolecular devices such as switches and motors. Naturally occurring or biological molecular machines are responsible for vital living processes such as DNA replication and ATP synthesis. Kinesins and ribosomes are examples of molecular machines, and they often take the form of multi-protein complexes. For the last several decades, scientists have attempted, with varying degrees of success, to miniaturize machines found in the macroscopic world. The first example of an artificial molecular machine (AMM) was reported in 1994, featuring a rotaxane with a ring and two different possible binding sites.
Diphosphene is a type of organophosphorus compound that has a phosphorus–phosphorus double bond, denoted by R-P=P-R'. These compounds are not common but are of theoretical interest. Normally, compounds with the empirical formula RP exist as rings. However, like other multiple bonds between heavy main-group elements, P=P double bonds can be stabilized by a large steric hindrance from the substitutions. The first isolated diphosphene bis(2,4,6-tri-tert-butylphenyl)diphosphene was exemplified by Masaaki Yoshifuji and his coworkers in 1981, in which diphosphene is stabilized by two bulky phenyl group.
Photochromism is the reversible transformation of a chemical species (photoswitch) between two forms by the absorption of electromagnetic radiation (photoisomerization), where the two forms have different absorption spectra. In plain language, this can be described as a reversible change of color upon exposure to light.
Chromium hexacarbonyl is a chromium(0) organometallic compound with the formula Cr(CO)6. It is a homoleptic complex, which means that all the ligands are identical. It is a colorless crystalline air-stable solid, with a high vapor pressure.
Norbornadiene is an organic compound and a bicyclic hydrocarbon. Norbornadiene is of interest as a metal-binding ligand, whose complexes are useful for homogeneous catalysis. It has been intensively studied owing to its high reactivity and distinctive structural property of being a diene that cannot isomerize. Norbornadiene is also a useful dienophile in Diels-Alder reactions.
Synthetic molecular motors are molecular machines capable of continuous directional rotation under an energy input. Although the term "molecular motor" has traditionally referred to a naturally occurring protein that induces motion, some groups also use the term when referring to non-biological, non-peptide synthetic motors. Many chemists are pursuing the synthesis of such molecular motors.
Solar chemical refers to a number of possible processes that harness solar energy by absorbing sunlight in a chemical reaction. The idea is conceptually similar to photosynthesis in plants, which converts solar energy into the chemical bonds of glucose molecules, but without using living organisms, which is why it is also called artificial photosynthesis.
A photoswitch is a type of molecule that can change its structural geometry and chemical properties upon irradiation with electromagnetic radiation. Although often used interchangeably with the term molecular machine, a switch does not perform work upon a change in its shape whereas a machine does. However, photochromic compounds are the necessary building blocks for light driven molecular motors and machines. Upon irradiation with light, photoisomerization about double bonds in the molecule can lead to changes in the cis- or trans- configuration. These photochromic molecules are being considered for a range of applications.
Nitrosobenzene is the organic compound with the formula C6H5NO. It is one of the prototypical organic nitroso compounds. Characteristic of its functional group, it is a dark green species that exists in equilibrium with its pale yellow dimer. Both monomer and dimer are diamagnetic.
Diimide, also called diazene or diimine, is a compound having the formula HN=NH. It exists as two geometric isomers, E (trans) and Z (cis). The term diazene is more common for organic derivatives of diimide. Thus, azobenzene is an example of an organic diazene.
Light-gated ion channels are a family of ion channels regulated by electromagnetic radiation. Other gating mechanisms for ion channels include voltage-gated ion channels, ligand-gated ion channels, mechanosensitive ion channels, and temperature-gated ion channels. Most light-gated ion channels have been synthesized in the laboratory for study, although two naturally occurring examples, channelrhodopsin and anion-conducting channelrhodopsin, are currently known. Photoreceptor proteins, which act in a similar manner to light-gated ion channels, are generally classified instead as G protein-coupled receptors.
A molecular switch is a molecule that can be reversibly shifted between two or more stable states. The molecules may be shifted between the states in response to environmental stimuli, such as changes in pH, light, temperature, an electric current, microenvironment, or in the presence of ions and other ligands. In some cases, a combination of stimuli is required. The oldest forms of synthetic molecular switches are pH indicators, which display distinct colors as a function of pH. Currently synthetic molecular switches are of interest in the field of nanotechnology for application in molecular computers or responsive drug delivery systems. Molecular switches are also important in biology because many biological functions are based on it, for instance allosteric regulation and vision. They are also one of the simplest examples of molecular machines.
In chemistry, a halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. Like a hydrogen bond, the result is not a formal chemical bond, but rather a strong electrostatic attraction. Mathematically, the interaction can be decomposed in two terms: one describing an electrostatic, orbital-mixing charge-transfer and another describing electron-cloud dispersion. Halogen bonds find application in supramolecular chemistry; drug design and biochemistry; crystal engineering and liquid crystals; and organic catalysis.
trans-Cyclooctene is a cyclic hydrocarbon with the formula [–(CH2)6CH=CH–], where the two C–C single bonds adjacent to the double bond are on opposite sides of the latter's plane. It is a colorless liquid with a disagreeable odor.
Stefan Hecht is a German chemist.
Photoelectrochemical processes are processes in photoelectrochemistry; they usually involve transforming light into other forms of energy. These processes apply to photochemistry, optically pumped lasers, sensitized solar cells, luminescence, and photochromism.
Photoactivated peptides are modified natural or synthetic peptides the functions of which can be activated with light. This can be done either irreversibly or in a reversible way. Caged peptides which contain photocleavable protecting groups belong to irreversibly activated peptides. Reversible activation/deactivation of peptide function are achieved by incorporation photo-controllable fragments in the side chains or in the backbone of peptide templates to get the photo-controlled peptides, which can reversibly change their structure upon irradiation with light of different wavelength. As the consequence, the properties, function and biological activity of the modified peptides can be controlled by light. Since light can be directed to specific areas, such peptides can be activated only at targeted sites. Azobenzenes, and diarylethenes can be used as the photoswitches. For therapeutic use, photoswitches with longer wavelengths or the use of two-photon excitation are required, coupled with improved methods for peptide delivery to live cells.