Photo-irradiated E/Z isomerization reaction of star-shaped isomers containing two cyanostilbene arms with charge transfer excited states†
The E/Z isomerization reaction of the multi-cyanostilbene molecule is still not clear. Herein, we have designed and synthesized three star-shaped molecular isomers with a triphenylamine core linked to two cyanostilbene groups with E/Z isomerization, Z,Z-TPDCF, Z,E-TPDCF and E,E-TPDCF, possessing three different isomeric molecular configurations, to investigate the specific E/Z isomerization reaction of the cyanostilbene groups in the two molecular arms. The in situ UV, 1H NMR and HPLC spectra under UV-irradiation clearly showed that the E/Z isomerization reactions of both E,E-TPDCF and Z,Z-TPDCF firstly turned them into Z,E-TPDCF, and the Z,E-TPDCF was almost simultaneously turned into more E,E-TPDCF and less Z,Z-TPDCF due to the calculated lowest unoccupied molecular orbitals of Z,E-TPDCF on the cyanostilbene arm with the Z-configuration. In general, Z,E-TPDCF exhibited a relatively better configurational stability than Z,Z-TPDCF or E,E-TPDCF under the photo-irradiation conditions. Further research demonstrated that all three isomers exhibited excellent aggregation-induced emission (AIE) properties.