Diarylethene
Diarylethene is the general name of a class of
Under the influence of light, these compounds can generally perform two kinds of reversible isomerizations:[1]
- E to Z isomerizations, most common for stilbenes (and azobenzenes). This process goes through an excited state energy minimum where the aromatic rings lie at 90° to each other. This conformation drops to the ground state and generally relaxes to trans and cis forms in a 1:1 ratio, thus the quantum yield for E-Z isomerization is very rarely greater than 0.5.
- 6π aromatic character of these groups.[2]The quantum yield of this reaction is generally less than 0.1, and in most diarylethenes the close-ring form is thermally unstable, reverting to the cis-form in a matter of seconds or minutes under ambient conditions.
Thermal isomerization is also possible. In E-Z isomerization, the thermal equilibrium lies well towards the trans-form because of its lower energy (~15 kJ mol−1 in stilbene).[3] The activation energy for thermal E-Z isomerization is 150–190 kJ mol−1 for stilbene, meaning that temperatures above 200°C are required to isomerize stilbene at a reasonable rate, but most derivatives have lower energy barriers (e.g. 65 kJ mol−1 for 4-aminostilbene). The activation energy of the electrocyclization is 73 kJ mol−1 for stilbene.
Both processes are often applied in molecular switches and for photochromism (reversible state changes from exposure to light).[4][5][6]
After the 6π electrocyclization of the Z form to the "close-ring" form, most unsubstituted diarylethenes are prone to
Stabilization of the closed-ring form to oxidation
One solution to the problem of oxidation is to replace the hydrogens
Dithienylethenes
Ortho-substitution of the aromatic units results in a stabilization against oxidation, but the closed-ring form still has a low thermodynamic stability in most cases (e.g. 2,3-dimesityl-2-butene has a half-life of 90 seconds at 20°C). This problem can be addressed by lowering the aromaticity of the system. The most commonly used example are the dithienylethenes, i.e. alkenes with a thiophene ring on either side.
Dithienylethene derivatives have shown different types of photochemical side reactions, e.g., oxidation or elimination reactions of the ring-closed isomer and formation of an annulated ring isomer as a byproduct of the photochromic reaction.
The dithienylethenes are also of interest for the fact that their isomerization requires very little change of shape. This means that their isomerization in a solid matrix can take place much more quickly than with most other
Applications
Typically, the open-ring isomers are colorless compounds, whereas the closed-ring isomers have colors dependent on their
References
- ^ H. Görner, J. Kuhn, Advances in Photochemistry 19, 1-117 (1995).
- ^ a b J. March, Advanced Organic Chemistry, 4th ed. (1992).
- J. Chem. Phys. 118:7823-7836 (2003) [1]
- Angew. Chem. Int. Ed. 2000, 39, 3348 [2].
- ^ B. L. Feringa (ed.), Molecular Switches, Wiley-VCH, 2001, Weinheim.
- Chem. Rev.: Memories and Switches.
- Chem. Rev.2000, 100, 1685.
- Chem. Commun. 747–750 (1999) [3]
- Phys. Chem. Chem. Phys. 16:18463-18471 (2014) [4]
- J. Am. Chem. Soc. 137 (7):2738–2747 (2015) [5]
- Angew. Chem. Int. Ed. 55: 1208 (2016) [6]
- ^ Chem. Rev.2000 , 100, 1685.
- ^ N. Katsonis, T. Kudernac, M. Walko, S. J. van der Molen, B. J. van Wees, B. L. Feringa, Advanced Materials 2006, 18, 1397–1400. [7]