Distortion‐Controlled Redshift of Organic Dye Molecules

It is shown, quantum chemically, how structural distortion of an aromatic dye molecule can be leveraged to rationally tune its optoelectronic properties. By using a quantitative Kohn–Sham molecular orbital (KS‐MO) approach, in combination with time‐dependent DFT (TD‐DFT), the influence of various structural and electronic tuning parameters on the HOMO–LUMO gap of a benzenoid model dye have been investigated. These parameters include 1) out‐of‐plane bending of the aromatic core, 2) bending of the bridge with respect to the core, 3) the nature of the bridge itself, and 4) π–π stacking. The study reveals the coupling of multiple structural distortions as a function of bridge length and number of bridges in benzene to be chiefly responsible for a decreased HOMO–LUMO gap, and consequently, red‐shifting of the absorption wavelength associated with the lowest singlet excitation (λ≈560 nm) in the model cyclophane systems. These physical insights together with a rational approach for tuning the oscillator strength were leveraged for the proof‐of‐concept design of an intense near‐infrared (NIR) absorbing cyclophane dye at λ=785 nm. This design may contribute to a new class of distortion‐controlled NIR absorbing organic dye molecules.