Adly Omima M I, Taha Ali, Fahmy Shery A, Ibrahim Magdy A
Department of Chemistry, Faculty of Education, Ain Shams University Roxy Cairo Egypt
RSC Adv. 2023 Sep 5;13(38):26587-26603. doi: 10.1039/d3ra05081e. eCollection 2023 Sep 4.
2-Aminochromone-3-carboxaldehyde (ACC) and its hydrazones (ACMHCA and ACMNPHTCA) with semicarbazide hydrochloride and -phenylthiosemicarbazide were synthesized and characterized by elemental analysis and spectral studies. The solvatochromic behavior of the title compounds in various solvents showed distinct bathochromic shifts on going from nonpolar to polar solvents, suggesting intramolecular-charge-transfer (ICT) solute-solvent interactions. The ground and excited state dipole moments of ACC, ACMHCA, and ACMNPHTCA were determined experimentally by the solvatochromic shift method using the Bilot-Kawski, Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet functions, and a microscopic Reichardt's solvent polarity parameter (). All the investigated molecules showed a substantial increase in the dipole moment upon excitation to the emitting state. The experimental results were generally consistent with the values obtained by the TD-DFT, B3LYP/6-311G++(d,p) method. Molecular electrostatic potential (MEP) mapping and natural charge and natural bonding orbital (NBO) analysis were performed and the results were discussed. The H NMR chemical shifts of the prepared compounds were simulated by the gage independent atomic orbital (GIAO) method and compared with their experimental chemical shift values. The biological activity data were correlated with the frontier molecular orbitals. The photovoltaic behavior of the title compounds showed there was sufficient electron injection.
合成了2-氨基色酮-3-甲醛（ACC）及其与盐酸氨基脲和对苯硫基氨基脲形成的腙（ACMHCA和ACMNPHTCA），并通过元素分析和光谱研究对其进行了表征。标题化合物在各种溶剂中的溶剂化显色行为表明，从非极性溶剂转变为极性溶剂时会出现明显的红移，这表明存在分子内电荷转移（ICT）溶质-溶剂相互作用。使用比洛特-考斯基、利珀特-马塔加、巴赫希耶夫、考斯基-查马-维亚莱特函数以及微观的赖夏德特溶剂极性参数，通过溶剂化显色位移法实验测定了ACC、ACMHCA和ACMNPHTCA的基态和激发态偶极矩。所有研究的分子在激发到发射态时偶极矩都有显著增加。实验结果与通过TD-DFT、B3LYP/6-311G++(d,p)方法获得的值总体一致。进行了分子静电势（MEP）映射以及自然电荷和自然键轨道（NBO）分析，并对结果进行了讨论。通过规范无关原子轨道（GIAO）方法模拟了所制备化合物的1H NMR化学位移，并将其与实验化学位移值进行了比较。将生物活性数据与前沿分子轨道相关联。标题化合物的光伏行为表明存在足够的电子注入。
