Design of Triads for Probing the Direct Through Space Energy Transfers in Closely Spaced Assemblies

Using a selective stepwise Suzuki cross-coupling reaction, two trimers built on three different chromophores were prepared. These trimers exhibit a D(^)A1-A2 structure where the donor D (octa-β-alkyl zinc(II)porphyrin either as diethylhexamethyl, 10a, or tetraethyltetramethyl, 10b, derivatives) through space transfers the S1 energy to two different acceptors, di(4-ethylbenzene) zinc(II)porphyrin (A1; acceptor 1) placed cofacial with D, and the corresponding free base (A2; acceptor 2), which is meso-meso-linked with A1. This structure design allows for the possibility of comparing two series of assemblies, 9a,b (D(^)A1) with 10a,b (D(^)Â1-A2), for the evaluation of the S1 energy transfer for the global process D*→A2 in the trimers. From the comparison of the decays of the fluorescence of D, the rates for through space energy transfer, kET for 10a,b (kET ≈ 6.4 × 10(9) (10a), 5.9 × 10(9) s(-1) (10b)), and those for the corresponding cofacial D(^)A1 systems, 9a,b, (kET ≈ 5.0 × 10(9) (9a), 4.7 × 10(9) s(-1) (9b)), provide an estimate for kET for the direct through space D*→A2 process (i.e., kET(D(^)A1-A2) - kET(D(^)A1) = kET(D*→A2) ∼ 1 × 10(9) s(-1)). This channel of relaxation represents ∼15% of kET for D*→A1.