Nitrogen Bridged Diazocines: Photochromes Switching within the Near-Infrared Region with High Quantum Yields in Organic Solvents and in Water

Diazocines are bridged azobenzenes with superior photophysical properties. In contrast to azobenzenes the Z configuration is thermodynamically stable and the E isomer is metastable. We present a new class of nitrogen bridged diazocines with bathochromically shifted switching wavelengths and remarkably high quantum yields (-NH-CH2- bridged diazocine: (Phi(Z -> E) = 0.57, Phi(E -> Z)= 0.8). Z to E isomerization is induced by irradiation with blue light, whereas switching back to the Z 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, photo switchable pharmacophores. The -NAc-CH2-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.