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While the influence of proquinoidal character upon the linear absorption spectrum of low optical bandgap π-conjugated polymers and molecules is well understood, its impact upon excited-state relaxation pathways and dynamics remains obscure. We report the syntheses, electronic structural properties, and excited-state dynamics of a series of model highly conjugated near-infrared (NIR)-absorbing chromophores based on a (porphinato)metal(ii)-proquinoidal spacer-(porphinato)metal(ii) ( PM-Sp-PM ) structural motif. A combination of excited-state dynamical studies and time-dependent density functional theory calculations: (i) points to the cardinal role that excited-state configuration interaction (CI) plays in determining the magnitudes of S 1 → S 0 radiative ( k  r ), S 1 → T 1 intersystem crossing ( k  ISC ), and S 1 → S 0 internal conversion ( k  IC ) rate constants in these PM-Sp-PM chromophores, and (ii) suggests that a primary determinant of CI magnitude derives from the energetic alignment of the PM and Sp fragment LUMOs (Δ E  L ). These insights not only enable steering of excited-state relaxation dynamics of high oscillator strength NIR absorbers to realize either substantial fluorescence or long-lived triplets ( τ  T 1  &gt; μs) generated at unit quantum yield ( Φ  ISC = 100%), but also crafting of those having counter-intuitive properties: for example, while (porphinato)platinum compounds are well known to generate non-emissive triplet states ( Φ  ISC = 100%) upon optical excitation at ambient temperature, diminishing the extent of excited-state CI in these systems realizes long-wavelength absorbing heavy-metal fluorophores. This work highlights approaches to: (i) modulate low-lying singlet excited-state lifetime over the picosecond-to-nanosecond time domain, (ii) achieve NIR fluorescence with quantum yields up to 25%, (iii) tune the magnitude of S 1 -T 1 ISC rate constant from 10 9 to 10 12 s -1 and (iv) realize T 1 -state lifetimes that range from ∼0.1 to several μs, for these model PM-Sp-PM chromophores, and renders new insights to evolve bespoke photophysical properties for low optical bandgap π-conjugated polymers and molecules based on proquinoidal conjugation motifs.

Controlling the excited-state dynamics of low band gap, near-infrared absorbers via proquinoidal unit electronic structural modulation