Understanding High Fluorescence Quantum Yield and Simultaneous Large Stokes Shift in Phenyl Bridged Donor-π-Acceptor Dyads with Varied Bridge Lengths in Polar Solvents.

Photophysical properties of electron donor-π-acceptor (D-π-A) dyads for a given pair of D and A highly depend on the π-bridge type and length and also on the solvent polarity. In this work, first-principles calculations with optimally tuned range-separated hybrids are implemented to explore and understand the optical absorption and emission properties of recently synthesized novel D-π-A dyads with 1,2-diphenylphenanthroimidazole (PPI) as D and 1,2,4-triazolopyridine (TP) as A with varied phenyl π-bridge lengths (denoted as PPI-P n -TP, n = 0-2 considered here) in solvents of different dielectrics. All three D-π-A dyads display almost an unaltered low-lying optical peak position and a red-shifted emission with increasing solvent polarity, corroborating well with the reported experimental observations. The observed emission shift was attributed to the stabilization of an intramolecular charge-transfer (ICT) state by the polar solvent. Contrastingly, our calculations reveal no ICT; rather the shift is essentially originated from the substantial excited-state relaxation involving primarily rotation of the PPI phenyl ring directly linked to the π-bridge, leading to an almost planarized emissive state. Further, the greater frontier molecular orbital delocalization-driven high fluorescence rate together with increased structural rigidity of the emissive state rationalize the observed high fluorescence quantum yield. The present research findings not only are helpful to better understand the reported experimental observations but also show routes to molecularly design functional D-π-A molecules for advanced optoelectronic, sensing, and biomedical applications.