AIE‐Active Ferrocene Appended Linear (D‐π‐A) Aromatic Ester Chromophores: Structural, Theoretical and Effect on Phenyl Ring on Luminescence and Nonlinear Optical Properties

Abstract In the present research, a new ferrocene‐appended linear donor‐π‐acceptor (D‐π‐A) ester chromophore Fc‐(C 6 H 4 ) 2 ‐COOC 2 H 5 ( 2 ) was synthesized and characterized using various spectroscopic techniques. The molecular structure of chromophore 2 was determined using single‐crystal X‐ray diffraction analysis, revealing its crystallization in the monoclinic crystal system with the P21/n space group. The chromophore Fc‐C 6 H 4 ‐COOC 2 H 4 ( 1 ) was utilized to compare its photophysical and nonlinear optical characteristics with those of 2 . Cyclic voltammetry revealed a single‐electron transfer mechanism from Fe 2+ ↔Fe 3+ . The emission solvatochromism studies show a polarized excited state in response to increasing solvent polarity, indicating charge transfer processes. Interestingly, in mixed aqueous media (THF/H 2 O), the chromophores exhibit intensified fluorescence due to restricted intra‐molecular rotation (RIR), despite weak emission in THF solvent. Chromophore 2 demonstrated 1.5 times higher second harmonic generation (SHG) efficiency than 1 , attributed to its extended π‐conjugation from an additional phenyl ring and reduced antiparallel alignments. Despite its centrosymmetric crystal packing, chromophore 2 exhibited SHG efficiency due to non‐covalent interactions (C−H⋅⋅⋅π) in the crystal lattice. Density Functional Theory (DFT) calculations, employing various functionals, provided insights into dipole moment and first hyperpolarizability, with B3LYP‐hybrid functional underestimating hyperpolarizability values owing to long‐range charge transfer interactions within the D‐π‐A systems, aligning closely with experimental findings.