Enhanced solvatochromic inversion in cationic stilbenes: Impact of π-extension on their solvent polarity sensitivity

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL Journal of Molecular Liquids Pub Date : 2025-02-01 Epub Date: 2024-12-30 DOI:10.1016/j.molliq.2024.126781

Ignacio Aburto , Matías Vidal , Raúl Mera-Adasme , Camila Pastenes , Carolina Aliaga , Moisés Domínguez

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Abstract

Two series of cationic stilbenes with different length of their π-systems were synthesized and their spectral response in a wide range of solvent polarities exhibited inverted solvatochromism, with an inversion point occurring in mildly polar solvents. The addition of the 1,4-phenylene unit in the charge-transfer pathway of the dyes caused a notable shift in the solvent polarity at which the solvatochromic inversion point occurred. Quantum mechanics calculations corroborated the experimental findings, demonstrating charge transfer from the HOMO to the LUMO, with the 1,4-phenylene unit affecting orbital distribution. Multiparametric analysis indicated that these spectral behaviors are the result of a compensation of the sensitivity of the extended dyes to solvent acidity by solvent basicity, polarizability, and dipolarity. This study highlights the importance of π-extension in tuning the solvatochromic response of cationic dyes.

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阳离子苯乙烯溶剂致变色反应的增强：π扩展对溶剂极性敏感性的影响

合成了两种不同π系长度的阳离子二苯乙烯，其光谱响应在较宽的溶剂极性范围内表现为反溶剂变色，在温和极性溶剂中出现反转点。在染料的电荷转移途径中加入1,4-苯基单元引起溶剂极性的显著变化，从而发生溶剂致变色反转点。量子力学计算证实了实验结果，证明电荷从HOMO转移到LUMO， 1,4-苯基单位影响轨道分布。多参数分析表明，这些光谱行为是溶剂碱度、极化率和双极性补偿染料对溶剂酸度敏感性的结果。本研究强调了π扩展在调节阳离子染料溶剂变色反应中的重要性。

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.