Tailoring Panchromatic Absorption and Excited-State Dynamics of Tetrapyrrole-Chromophore (Bodipy, Rylene) Arrays - Interplay of Orbital Mixing and Configuration Interaction

Three sets of tetrapyrrole-chromophore arrays have been examined that exhibit panchromatic absorption across large portions of the near-ultraviolet (NUV) to near-infrared (NIR) spectrum along with favorable excited-state properties for use in solar-energy conversion. The arrays vary the tetrapyrrole (porphyrin, chlorin, bacteriochlorin), chromophore (boron-dipyrrin, perylene, terrylene), and attachment sites (meso-position, β-pyrrole position). In all, seven dyads, one triad, and nine benchmarks in toluene and benzonitrile were studied using steady-state and time-resolved absorption and fluorescence spectroscopy. The results were analyzed with the aid of density functional theory (DFT) and time-dependent DFT calculations. Natural transition orbitals (NTOs) were constructed to assess the net change in electron density associated with each NUV-NIR absorption transition. The porphyrin-perylene dyad P-PMI displays the most even spectral coverage from 400 to 700 nm, with an average ϵ ∼ 43 000 M^-1 cm^-1. A significant contributor is a chromophore-induced reduction in the configuration interaction involving the four frontier molecular orbitals of benchmark porphyrins and associated constructive/destructive transition-dipole interference that results in intense (ϵ ∼ 400 000 M^-1 cm^-1) NUV and weak (<20 000 M^-1 cm^-1) visible features. P-PMI has an S₁ lifetime (τ_S) of 4.7 ns in toluene and 1.3 ns in benzonitrile. Bacteriochlorin analogue BC-PMI has more extended spectral coverage (350-750 nm) and τ_S = 2.8 ns in toluene and 30 ps in benzonitrile. Terrylene analogue P-TMI has intermediate optical characteristics with τ_S = 310 ps in toluene and 150 ps in benzonitrile. The NTOs for most arrays show that S₀ → S₁ primarily involves the tetrapyrrole, but for P-TMI the NTOs have electron density delocalized over the two units as a result of extensive orbital mixing. Collectively, the insights obtained should aid the design of tetrapyrrole-based architectures for panchromatic light-harvesting systems for solar-energy conversion.