Scholarlink

<p>The optical and energy storage characteristics of the diazaborolo[3,4-a]quinolin-2(1&#xa0;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&#xa0;eV). Pronounced electrophilic character at the BF<sub>2</sub>-coordinated azo nitrogen and strong nucleophilic character at the terminal donor moiety were revealed by the dual descriptor (Δ<i>f</i> = <i>f</i>⁺- <i>f</i>⁻), confirming the preferred intramolecular charge-transfer pathway. Reflecting enhanced solvent-stabilized intramolecular charge transfer, the main absorption (red shifted) band appeared at 664&#xa0;nm, in toluene at 738.35&#xa0;nm, and in acetonitrile at 745.85&#xa0;nm. Exceeding 0.79 in light-harvesting efficiency and decreasing to 11.32 <i>ns</i> in radiative lifetime, the results indicate efficient photoexcitation and emission. Remarkably, the first hyperpolarizability (<i>β</i><sub>tot</sub>) exhibited strong solvent dependence, rising from 4.355 × 10⁻<sup>29</sup> esu in the acetonitrile to 169.551 × 10⁻<sup>29</sup> esu, demonstrating the outstanding nonlinear optical performance of ABS12. The first-order electro-optic (Pockels) coefficient <i>β</i> (-ω, ω, 0) as well as the second-order nonlinear optical coefficient <i>β</i> (-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-BF<sub>2</sub> 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.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Solvent, substituent and external field effects on isomerism, absorption, and polarizability of boron‑phenyldiazenyl derivatives: a donor-acceptor approach to reversible energy storage

  • 期刊论文

  • 发表日期：

    2026年7月31日

查看全文
  • Muhammad Ibrahim,
  • Afifa Yousuf,
  • Muhammad Zahid Qureshi,
  • Muhammad Arshad,
  • Muhammad Arif Ali

摘要

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.