Arylethynyl derivatives of the dihydroazulene/vinylheptafulvene photo/thermoswitch: tuning the switching event.
A selection of dihydroazulene (DHA) photoswitches incorporating an arylethynyl-substituent in the seven-membered ring was prepared by palladium-catalyzed Sonogashira cross-coupling reactions employing a suitable bromo-functionalized DHA. Shielding of the alkyne bridge and separating the aryl and DHA units, by sterically demanding groups, was required to obtain stable compounds. The DHAs underwent a light-induced ring-opening to vinylheptafulvenes (VHFs) which were thermally converted to a mixture of two DHA regioisomers, one of which was the original one. The influence of the aryl groups on the DHA and VHF absorptions and on their interconversion was investigated in detail. The rates of the switching events were finely tuned by the donor or acceptor strength of the aryl group. The thermal ring closure was found to proceed most readily in the presence of an electron-donating group on the seven-membered ring. The rate constant was found to follow a Hammett linear free energy correlation, which signals that stabilization of a positive charge in the seven-membered ring plays a crucial role in the ring-closure reaction. In view of these findings, it was possible to control the switching event by protonation/deprotonation of an anilino-substituted DHA. Also, the light-induced ring opening reaction was strongly controlled by acid/base. In addition to the mesomeric effects exerted by an arylethynyl group, the inductive effects exerted by different groups on the thermal ring closure were elucidated. Although the alkyne bridge transmits the electronic character of the aryl group, the ring-closure is retarded for all the ethynylated compounds relative to the parent unsubstituted compound. Along with our synthesis of suitable arylalkynes, we discovered an interesting byproduct in a Sonogashira cross-coupling reaction involving a nitrophenyl group, namely a diaryl azoxy compound. Its structure was confirmed by X-ray crystallographic analysis.
Broman
Søren Lindbaek
SL
Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark.
Petersen
Michael Axman
MA
Tortzen
Christian G
CG
Kadziola
Anders
A
Kilså
Kristine
K
Nielsen
Mogens Brøndsted
MB