Tuning the Thermal Stability and Photoisomerization of Azoheteroarenes through Macrocycle Strain

Abstract

<p>Azobenzene and its derivatives are one of the most-widespread molecular scaffolds in a range of modern applications, as well as in fundamental research. After photoexcitation, azo-based photoswitches revert back to the most stable isomer in a timescale (t<sub>1/2</sub>) that determines the range of potential applications. Attempts to bring t<sub>1/2</sub> to extreme values prompted to the development of azobenzene and azoheteroarene derivatives that either rebalance the E- and Z- isomer stabilities, or exploit unconventional thermal isomerization mechanisms. In the former case, one successful strategy has been the creation of macrocycle strain, which tends to impact the E/Z stability asymmetrically, and thus significantly modifies t<sub>1/2</sub>. On the bright side, bridged derivatives have shown an improved optical switching owing to the higher quantum yields and absence of degradation. However, in most (if not all) cases, bridged derivatives display a <i>reversed</i> thermal stability (more stable Z-isomer), and smaller t<sub>1/2</sub> than the acyclic counterparts, which restricts their potential interest to applications requiring a fast forward and backwards switch. In this paper, we investigate the impact of alkyl bridges to the thermal stability of phenyl-azoheteroarenes using computational methods, and we reveal that is indeed possible to combine such improved photo-switching characteristics while preserving the <i>regular</i> thermal stability (more stable E-isomer), and increased t<sub>1/2</sub> values under the appropriate connectivity and bridge length.</p>

Towards low-energy-light-driven bistable photoswitches: ortho-fluoroaminoazobenzenes

“…We also considered the rotational pathway for all selected molecules applying broken-symmetry UDFT. The rotational transition states (with the CNNC dihedral of about 90° and both CNN units bent) are expected to exhibit homolytic cleavage of the azo bond and, therefore, RDFT is expected to fail 68,69 . Interestingly, for the recently introduced azobispyrazole family mentioned above the rotational barriers calculated with UDFT were found to be lower than the experimental ones, in contrast to the inversion barriers (see above) 66 .…”