Popis: |
π-Stacking is the most common structural feature that dictates the optical and electronic properties of chromophores in the solid state. Herein, a unidirectional singlet–singlet energy-transfer dyad has been designed to test the effect of π-stacking of zinc(II) porphyrin, [Zn2], as a slipped dimer acceptor using a BODIPY unit, [bod], as the donor, bridged by the linker C6H4C≡CC6H4. The rate of singlet energy transfer, kET(S1), at 298 K (kET(S1) = 4.5 × 1010 s–1) extracted through the change in fluorescence lifetime, τF, of [bod] in the presence (27.1 ps) and the absence of [Zn2] (4.61 ns) from Streak camera measurements, and the rise time of the acceptor signal in femtosecond transient absorption spectra (22.0 ps), is faster than most literature cases where no π-stacking effect exists (i.e., monoporphyrin units). At 77 K, the τF of [bod] increases to 45.3 ps, indicating that kET(S1) decreases by 2-fold (2.2 × 1010 s–1), a value similar to most values reported in the literature, thus suggesting that the hi... |