urRehman Shafiq, Fatima Saliha, Muhammad Shabbir, Bibi Shamsa, Munawar Khurram Shahzad, Al-Sehemi Abdullah G, Chaudhry Aijaz Rasool, Adnan Muhammad
Department of Chemistry, University of Agriculture Faisalabad, Faisalabad, 38000, Pakistan.
Department of Chemistry, College of Science, King Khalid University, Abha, 61413, P.O. Box 9004, Abha, 61413, Saudi Arabia.
J Mol Graph Model. 2024 May;128:108723. doi: 10.1016/j.jmgm.2024.108723. Epub 2024 Feb 5.
Nonlinear optical (NLO) response materials are among the smartest materials of the era and are employed to modulate the phase and frequency of the laser. The present study presents a quantum chemical framework for tailoring nitrogen/boron doped derivatives of Dihydrodibenzo [de,op]pentacene through terminal and central core modifications. The derivatives of these compounds have been designed by introducing various π-conjugated connectors as well as B/N heteroatoms in the phenalene rings. Density functional theory (DFT) methods are used to optimize the ground state molecular geometries of designed compounds, represented as 1 to 4 (phenalene derivatives) and 1-BN to 4-BN (B/N doped phenalene derivatives) at the M06-2X/6-311G* level of theory. The highest value of 116.9 × 10 esu and 240.2 × 10 esu for isotropic and anisotropic linear polarizability is shown by compound 4. Among the designed compounds, 4-BN has achieved the highest γ amplitude of 1858 × 10 esu owing to its unique molecular structural design. Further analysis of electronic parameters, such as electron density difference (EDD) maps, the density of states, electrostatic potentials, transition density matrix (TDM) analysis, and frontier molecular orbitals analysis (FMOs), demonstrated the more effective intramolecular charge transfer (ICT) for the best compounds, resulting in a good NLO response. The compounds were also analyzed for their potential in photovoltaic applications based on factors such as open circuit voltage values determined to be between (0.14 eV and 1.82 eV), and light harvesting efficiency (0.425-0.909).
非线性光学（NLO）响应材料是这个时代最智能的材料之一，用于调制激光的相位和频率。本研究提出了一个量子化学框架，用于通过末端和中心核心修饰来定制二氢二苯并[de,op]并五苯的氮/硼掺杂衍生物。这些化合物的衍生物是通过在并苯环中引入各种π共轭连接体以及B/N杂原子来设计的。采用密度泛函理论（DFT）方法，在M06 - 2X/6 - 311G*理论水平下优化所设计化合物的基态分子几何结构，这些化合物表示为1至4（并苯衍生物）和1 - BN至4 - BN（B/N掺杂并苯衍生物）。化合物4表现出各向同性和各向异性线性极化率的最高值，分别为116.9×10 esu和240.2×10 esu。在所设计的化合物中，4 - BN由于其独特的分子结构设计，实现了1858×10 esu的最高γ振幅。通过对电子密度差（EDD）图、态密度、静电势、跃迁密度矩阵（TDM）分析和前线分子轨道分析（FMOs）等电子参数的进一步分析，证明了最佳化合物具有更有效的分子内电荷转移（ICT），从而产生良好的NLO响应。还基于诸如开路电压值在（0.14 eV至1.82 eV之间）以及光捕获效率（0.425 - 0.909）等因素，分析了这些化合物在光伏应用中的潜力。
