Dyads with tunable near-infrared donor–acceptor excited-state energy gaps: molecular design and Förster analysis for ultrafast energy transfer
Literature Information
Haoyu Jing, Nikki Cecil M. Magdaong, James R. Diers, Christine Kirmaier, David F. Bocian, Dewey Holten, Jonathan S. Lindsey
Bacteriochlorophylls, nature's near-infrared absorbers, play an essential role in energy transfer in photosynthetic antennas and reaction centers. To probe energy-transfer processes akin to those in photosynthetic systems, nine synthetic bacteriochlorin–bacteriochlorin dyads have been prepared wherein the constituent pigments are joined at the meso-positions by a phenylethyne linker. The phenylethyne linker is an unsymmetric auxochrome, which differentially shifts the excited-state energies of the phenyl- or ethynyl-attached bacteriochlorin constituents in the dyad. Molecular designs utilized known effects of macrocycle substituents to engineer bacteriochlorins with S0 → S1 (Qy) transitions spanning 725–788 nm. The design-predicted donor–acceptor excited-state energy gaps in the dyads agree well with those obtained from time dependent density functional theory calculations and with the measured range of 197–1089 cm−1. Similar trends with donor–acceptor excited-state energy gaps are found for (1) the measured ultrafast energy-transfer rates of (0.3–1.7 ps)−1, (2) the spectral overlap integral (J) in Förster energy-transfer theory, and (3) donor–acceptor electronic mixing manifested in the natural transition orbitals for the S0 → S1 transition. Subtle outcomes include the near orthogonal orientation of the π-planes of the bacteriochlorin macrocycles, and the substituent-induced shift in transition-dipole moment from the typical coincidence with the NH–NH axis; the two features together afforded the Förster orientation term κ2 ranging from 0.55–1.53 across the nine dyads, a value supportive of efficient excited-state energy transfer. The molecular design and collective insights on the dyads are valuable for studies relevant to artificial photosynthesis and other processes requiring ultrafast energy transfer.
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