New Acylhydrazone Photoswitches with Quantitative Conversion and High Quantum Yield but without Hydrogen Bond Stabilizing (Z)-Isomer

摘要

Hydrazones are recently attracting increasing interest because of their facile synthesis and high addressability, fatigue resistance, and modifiability as molecular switches. However, this new class of switches generally suffers from low conversion from E- to Z-configuration. Here, novel benzoylhydrazones were synthesized by condensation of 2-methoxynaphthaldhyde and benzoylhydrazine. In this hydrazone system, both sides of the imine double bond had large steric hindrance, so that the (E)-isomer of the benzoylhydrazones was less stable and easily converted into the (Z)-isomer even without an intramolecular hydrogen bond. Up to 99% conversion efficiency and 89% quantum yield were obtained, in addition to excellent addressability and high fatigue resistance. Outstandingly,. the crystal structure of one (Z)-isomer disclosed no intermolecular hydrogen bonds between the molecules of the (Z)-isomer but strong and sequential hydrogen bonds between those of the (E)-isomer. Therefore, the (E)-isomer was less soluble in solvents than the (Z)-isomer. This molecular switch system could be easily modified by both hydrophilic pentaethylene glycol chains and hydrophobic octyl chains. Under light irradiation, the resultant amphiphilic acylhydrazone could be transferred from (E)-isomer to (Z)-isomer in more than 90% yield even in water after light irradiation. Meanwhile, the self-assembled big nanospheres could rearrange into much smaller vesicles because of the solubility difference of (Z)- and (E)-isomers. After the anticancer drug procarbazine was loaded by this kind of acylhydrazone in water, it could be released by light irradiation, showing potential application in photocontrollable drug release.