A push-pull unsymmetrical subphthalocyanine dimer

作者:Zango German; Zirzlmeier Johannes; Claessens Christian G; Clark Timothy*; Victoria Martinez Diaz M; Guldi Dirk M; Torres Tomas
来源:Chemical Science, 2015, 6(10): 5571-5577.
DOI:10.1039/c5sc01709b

摘要

Unsymmetrical subphthalocyanine fused dimers have been prepared from appropriate ortho-dinitrile SubPc precursors. In particular, either electron-donating or electron-accepting substituents have been introduced on each SubPc constituent unit, resulting in unprecedented push-pull pi-extended curved aromatic macrocycles. From fluorescence experiments in solvents of different polarity we conclude a dual fluorescence, namely a delocalized singlet excited state (1.73 eV) and a polarized charge transfer state (<1.7 eV). Pump probe experiments corroborate the dual nature of the fluorescence. On one hand, the delocalized singlet excited state gives rise to a several nanosecond lasting intersystem crossing yielding the corresponding triplet excited state. On the other hand, the polarized charge transfer state deactivates within a few picosesonds. Visualization of the charge transfer state was accomplished by means of molecular modeling with a slight polarization of the HOMO towards the electron donor and of the LUMO towards the electron acceptor.

  • 出版日期2015