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Solvent, substituent and external field effects on isomerism, absorption, and polarizability of boron‑phenyldiazenyl derivatives: a donor-acceptor approach to reversible energy storage
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DOI：10.1007/s11082-026-09049-y.png)
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Abstract
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The optical and energy storage characteristics of the diazaborolo[3,4-a]quinolin-2(1 H)-imine based photo-switches (ABS). The twelve derivatives were designed and studied in gas and solvent phases (toluene and acetonitrile) through a comprehensive quantum-chemical investigation. The planarity and extended π-conjugation of ABS was explored, to explore ICT and light absorption behavior. Frontier molecular orbital (FMO) analysis was employed to reveal a reduced HOMO-LUMO energy gap (3.15 eV). Pronounced electrophilic character at the BF2-coordinated azo nitrogen and strong nucleophilic character at the terminal donor moiety were revealed by the dual descriptor (Δf = f⁺- f⁻), confirming the preferred intramolecular charge-transfer pathway. Reflecting enhanced solvent-stabilized intramolecular charge transfer, the main absorption (red shifted) band appeared at 664 nm, in toluene at 738.35 nm, and in acetonitrile at 745.85 nm. Exceeding 0.79 in light-harvesting efficiency and decreasing to 11.32 ns in radiative lifetime, the results indicate efficient photoexcitation and emission. Remarkably, the first hyperpolarizability (βtot) exhibited strong solvent dependence, rising from 4.355 × 10⁻29 esu in the acetonitrile to 169.551 × 10⁻29 esu, demonstrating the outstanding nonlinear optical performance of ABS12. The first-order electro-optic (Pockels) coefficient β (-ω, ω, 0) as well as the second-order nonlinear optical coefficient β (-2ω, ω, ω) induced by an electric field were also strongly amplified in polar solvents, highlighting ABS12 as a promising electro-optic and frequency-doubling material. Furthermore, the donor-acceptor structural modifications improve the isomerization characteristics of the parent Azo-BF2 framework by promoting a more favorable molecular configuration, which facilitates intramolecular charge transfer and contributes to the enhanced nonlinear optical response of the designed derivatives. Overall, the combined electronic, reactivity, and nonlinear-optical descriptors demonstrate that ABS12 is an outstanding visible-light-responsive photo switches with exceptional electro-optic and photonic energy-storage potential.
Keywords:
Boron-phenyldiazenyl
Solvent effect
UV-Vis absorption
External electric field
First hyperpolarizability (β)
Reversible energy storage
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