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 (Q_y) 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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