Luo Leixing, Dang Mingxuan, Song Xiaoming, Zhao Qingxia, Yang Shuo, Hou Xiufang, Liu Shuai, Ren Yixia
Shaanxi Key Laboratory of Chemical Reaction Engineering, Laboratory of New Energy and New Function Materials, College of Chemistry and Chemical Engineering, Yan'an University, Yan'an, 716000, Shaanxi, China.
China Railway Shanghai Group Co., Ltd. Shanghai Large Scale Road Maintenance Machinery Operation and Maintenance Section, Jing'an, Shanghai, 200071, China.
J Mol Model. 2025 Apr 29;31(5):148. doi: 10.1007/s00894-025-06366-z.
This study explored the geometry, aromaticity, electrostatic potential, and fluorescence sensing capability of N,N'-dimethyl naphthodithiophene diimide (C-NDTI-S) and its derivatives (C-NDFI-O and C-NDPI-N), where thiophene rings were substituted with furan and pyrrole, respectively. Theoretical calculations revealed that C-NDTI-S had the most negative adsorption energy for 2,4,6-trinitrophenol (TNP), and its electronic absorption spectrum and fluorescence spectrum decreased considerably upon TNP adsorption. Through FMO, hole-electron, independent gradient model, and energy decomposition analysis, it was revealed that the essence of fluorescence quenching is the intermolecular weak π-π interaction driving photo-induced electron transfer. Furthermore, C-NDFI-O and C-NDPI-N generated by modifying the structure of C-NDTI-S have the potential to serve as more efficient fluorescent sensors for TNP detection. The fluorescence recovery times confirmed the suitability of the three compounds as fluorescence probes.
In this study, the Gaussian 09 software package at B3LYP-D3(BJ)/6-311 + + G** level was applied to optimize the structure, energy, and fluorescence recovery time. Multiwfn combined with VMD software package was used to analyze the aromaticity of compounds using LOL-π and HOMA, with a focus on the differences in aromaticity after thiophene was substituted with different rings. Using AMBER force field for energy decomposition analysis based on force field (EDA-FF), the weak intermolecular interaction components are decomposed. The independent gradient model analysis based on Hirshfeld partition analysis clearly demonstrates the π-π interactions between molecules, with the δ parameter set to 0.005 a.u. Electron absorption spectroscopy, charge-transfer spectra spectroscopy, molecular interactions, and hole electron interactions were all completed with the help of Multifwn software.
本研究探索了N，N'-二甲基萘并二噻吩二酰亚胺（C-NDTI-S）及其衍生物（C-NDFI-O和C-NDPI-N）的几何结构、芳香性、静电势和荧光传感能力，其中噻吩环分别被呋喃和吡咯取代。理论计算表明，C-NDTI-S对2,4,6-三硝基苯酚（TNP）具有最负的吸附能，并且其电子吸收光谱和荧光光谱在吸附TNP后显著下降。通过前线分子轨道（FMO）、空穴-电子、独立梯度模型和能量分解分析，揭示了荧光猝灭的本质是分子间弱π-π相互作用驱动的光致电子转移。此外，通过修饰C-NDTI-S的结构生成的C-NDFI-O和C-NDPI-N有潜力作为更高效的用于TNP检测的荧光传感器。荧光恢复时间证实了这三种化合物作为荧光探针的适用性。
在本研究中，使用B3LYP-D3(BJ)/6-311++G**水平的高斯09软件包来优化结构、能量和荧光恢复时间。使用Multiwfn结合VMD软件包，利用LOL-π和HOMA分析化合物的芳香性，重点关注噻吩被不同环取代后的芳香性差异。使用基于分子力场的能量分解分析（EDA-FF），采用AMBER分子力场分解弱分子间相互作用成分。基于Hirshfeld划分分析的独立梯度模型分析清楚地展示了分子间的π-π相互作用，δ参数设置为0.005 a.u.。电子吸收光谱、电荷转移光谱、分子相互作用和空穴-电子相互作用均借助Multifwn软件完成。
