DFT studies of a novel phenothiazine-based fluorescent probe (PFP) for its physiochemical and thermodynamic properties

IF 2.2 4区 化学 Q2 Engineering
Mukhtiar Ali, Abdul Rehman Jatoi, Jawad Ahmed, Sidra Mushtaq, Faheem Akhter, Mansoor Ahmed Lakhmir, Muhammad Junaid Ahsan, Haris Jawad Arain
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Abstract

Herein, DFT studies were carried out of a novel Phenothiazine-based Fluorescent Probe (PFP) for its physio-chemical and thermodynamic properties. Various aspects were investigated including optimized geometry, frontier molecular orbitals, molecular electrostatic potential, density of states, UV-Vis emission spectra and reactivity parameters. DFT studies reveal that molecular modeling, including the optimization of molecular structures like PFP, is crucial for understanding complex molecules and their characteristics. The energy difference (∆E) between the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) was determined to be 4.48 eV. MEP maps indicate the nitrogen and sulfur atoms in the thiazine ring appear red, indicating high electron density. Similarly, the benzene rings appear blue thereby indicating lower electron density. The DOS spectrum confirmed the HOMO-LUMO gap and provided insights into the availability of electronic states at specific energy levels. High DOS intensity indicated many accessible states, while zero intensity indicated none. Time-Dependent Density Functional Theory (TD-DFT) calculations predicted the absorption maximum at 365 nm and emission spectra for PFP, with a calculated maximum emission at 656 nm. Coordination with water shifts the emission to 690 nm, showing a redshift of 44 nm. Moreover, the theoretically calculated maximum emission of probe PFP was determined to be λem = 656 nm, whereas maximum emission spectra of probe PFP with water coordination is calculated as λem = 690 nm which is red shifted 44 nm. These theoretically calculated values significantly deviate from experimental value. This deviation occured because the absorption and emission spectra recorded in solvents of different polarity result in different wavenumbers and intensities.

Graphical abstract

新型吩噻嗪基荧光探针 (PFP) 的物理化学和热力学性质的 DFT 研究
在此,我们对新型吩噻嗪基荧光探针(PFP)的物理化学和热力学性质进行了 DFT 研究。研究涉及多个方面,包括优化几何形状、前沿分子轨道、分子静电位、状态密度、紫外-可见发射光谱和反应性参数。DFT 研究表明,分子建模(包括 PFP 等分子结构的优化)对于理解复杂分子及其特性至关重要。最高占位分子轨道(HOMO)和最低未占位分子轨道(LUMO)之间的能差(ΔE)被确定为 4.48 eV。MEP 图显示,噻嗪环中的氮原子和硫原子呈现红色,表明电子密度较高。同样,苯环呈现蓝色,表明电子密度较低。DOS 光谱证实了 HOMO-LUMO 间隙,并提供了对特定能级上电子状态可用性的深入了解。高 DOS 强度表示有许多可访问的状态,而零强度则表示没有可访问的状态。与时间相关的密度泛函理论(TD-DFT)计算预测了全氟辛烷磺酸在 365 纳米波长处的最大吸收光谱和发射光谱,计算得出的最大发射光谱为 656 纳米波长。与水配位后,发射波长变为 690 纳米,红移 44 纳米。此外,探针全氟碳化物的理论计算最大发射值为 λem = 656 纳米,而与水配位的探针全氟碳化物的最大发射光谱计算值为 λem = 690 纳米,红移 44 纳米。这些理论计算值与实验值有很大偏差。出现这种偏差的原因是在不同极性的溶剂中记录的吸收和发射光谱会产生不同的波长和强度。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemical Papers
Chemical Papers Chemical Engineering-General Chemical Engineering
CiteScore
3.30
自引率
4.50%
发文量
590
期刊介绍: Chemical Papers is a peer-reviewed, international journal devoted to basic and applied chemical research. It has a broad scope covering the chemical sciences, but favors interdisciplinary research and studies that bring chemistry together with other disciplines.
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