Otto Diels-Institute of Organic Chemistry , Christian Albrechts University Kiel , Otto Hahn Platz 4 , 24118 Kiel , Germany.
Institute of Physical and Theoretical Chemistry , Graz University of Technology , Stremayrgasse 9 , 8010 Graz , Austria.
J Am Chem Soc. 2019 Aug 28;141(34):13592-13600. doi: 10.1021/jacs.9b06104. Epub 2019 Aug 15.
Diazocines are bridged azobenzenes with superior photophysical properties. In contrast to azobenzenes the configuration is thermodynamically stable and the isomer is metastable. We present a new class of nitrogen bridged diazocines with bathochromically shifted switching wavelengths and remarkably high quantum yields (-NH-CH- bridged diazocine: Φ = 0.57, Φ = 0.8). to isomerization is induced by irradiation with blue light, whereas switching back to the isomer is accomplished with light in the near-infrared window (up to 740 nm), which is important for medical applications like photopharmacology (deep tissue penetration). Furthermore, substitution at the bridging nitrogen should provide access to widely applicable tricyclic, photoswitchable pharmacophores. The -NAc-CH- bridged derivative is soluble in water, and all photophysical properties (conversion rates, quantum yields, and thermal half-lives) are largely retained. Hence, this diazocine is an ideal photoswitch for applications in biochemical systems and in photopharmacology.
重氮嗪是一种具有优越光物理性质的桥联偶氮苯。与偶氮苯相比，其反式构型热力学稳定，顺式异构体亚稳。我们提出了一类新型氮桥联重氮嗪，其开关波长红移，量子产率显著提高（-NH-CH-桥联重氮嗪：Φ = 0.57，Φ = 0.8）。顺式到反式的异构化是由蓝光照射诱导的，而反式到顺式的转换则可以用近红外光（高达 740nm）完成，这对于光药理学（深层组织穿透）等医学应用非常重要。此外，在桥接氮原子上的取代应该可以得到广泛应用的三环、光致可切换的药效团。-NAc-CH-桥联衍生物在水中具有良好的溶解性，所有光物理性质（转换速率、量子产率和热半衰期）都得到了很大的保留。因此，这种重氮嗪是生化系统和光药理学应用中的理想光开关。
