Solvent-Assisted Prototopic Switching of Norharmane Along Hydrogen-Bonded Network: Assessing the Precise Length of Network

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC
Suvendu Paul, Nilanjan Dey
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Abstract

In this article, the proton transfer dynamics along a stable norharmane•(H2O)n (n = 2–4) hydrogen-bonded cluster on conversion from the neutral to cationic form of norharmane (NHM) in water medium was demonstrated experimentally and theoretically. The distinct absorption and emission bands of different prototropic forms of NHM are well-known in the literature. Initially, the conversion from neutral to cationic form of NHM on moving from a polar aprotic (acetonitrile) to a polar protic (water) solvent was ensured by steady-state absorption and fluorescence studies. The analysis of IR spectra and steady-state anisotropy data of NHM confirmed the possibility of the formation of a hydrogen-bonded network in the presence of water. The length of the network was explored and assumed by extensive Density Functional Theory (DFT) calculations. Then, by time-dependent density functional theory (TD-DFT), the excited state proton transfer (ESPT) pathway was established interrogating the NHM-water cluster with different numbers of water molecules. The theoretical analysis assured that the NHM•(H2O)2 cluster was incapable of maintaining the stable hydrogen bonding wire in the course of the ESPT mechanism. Rather, NHM•(H2O)3 and NHM•(H2O)4 clusters were simultaneously involved in operating the ESPT mechanism. The NHM•(H2O)4 cluster was more feasible to carry out the proton transfer than the NHM•(H2O)3 cluster. To the best of our knowledge, this was possibly the first theoretical evidence behind the conversion from neutral to cationic form of NHM via the formation of a hydrogen-bonded network.

Abstract Image

溶剂辅助Norharmane沿氢键网络的原型交换:网络精确长度的评估
本文从实验和理论两方面论证了稳定的诺哈曼•(H2O)n (n = 2-4)氢键簇中诺哈曼(NHM)在水介质中由中性形态转化为阳离子形态的质子转移动力学。不同原始形态的NHM具有不同的吸收和发射带,这在文献中是众所周知的。最初,NHM从极性非质子(乙腈)到极性质子(水)溶剂从中性到阳离子形式的转化是通过稳态吸收和荧光研究来保证的。红外光谱和稳态各向异性数据的分析证实了NHM在有水存在时形成氢键网络的可能性。通过密度泛函理论(DFT)的计算,对网络的长度进行了探索和假设。然后,利用时间依赖密度泛函理论(TD-DFT)建立了不同水分子数的nhm -水团簇的激发态质子转移(ESPT)途径。理论分析证实了NHM•(H2O)2簇在ESPT机制过程中无法维持氢键丝的稳定。相反,NHM•(H2O)3和NHM•(H2O)4簇同时参与了ESPT机制的运行。NHM•(H2O)4团簇比NHM•(H2O)3团簇更容易进行质子转移。据我们所知,这可能是NHM通过形成氢键网络从中性形式转化为阳离子形式的第一个理论证据。
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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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