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Density functional theoretical tailoring of electronic effect through various substituents on calix[4]arene‐crown‐6 for efficient Cs+ ion encapsulation and extraction
International Journal of Quantum Chemistry ( IF 2.2 ) Pub Date : 2020-08-25 , DOI: 10.1002/qua.26436
Anil Boda 1 , Sk. Musharaf Ali 1
Affiliation  

The structure, energetic, and quantum chemical descriptors of Cs+ complexes of calix[4]arene‐crown‐6 (C4C6) and substituted C4C6, that is, 1,3 alternate‐diethoxy C4C6, are reported here based on the analysis of results obtained using density functional theory (DFT). Substitution of benzo group in both C4C6 and 1,3 alternate‐diethoxy C4C6 resulted in a reduction of binding energy (BE). Further substitution of the benzo group with methyl, methoxy, and amino groups leads to an increase in BE, and nitro substitution leads to decrease in BE for C4C6, whereas in the case of 1,3 alternate‐diethoxy calix[4]arenebenzocrown‐6, methoxy substitution leads to the highest BE compared to other complexes. The calculated Gibbs free energy, ΔGgas also followed the same order as BE in the case of 1,3 alternate‐diethoxy C4C6 and their substituted ligands. Furthermore, the ΔG of complexation was computed using a thermodynamic cycle with conductor‐like screening model in different solvents: toluene, chloroform, octanol, and nitrobenzene. The values of ΔGext are found to be increased with an increase in the dielectric constant of the solvent and were found to be highest in the nitrobenzene. The atoms in molecule analysis reveals partial ionic character in the CsO bond. Among all the studied complexes, 1,3 alternate‐diethoxy calix[4]arene 3′‐methoxy benzo crown‐6 displays highest ΔGext in nitrobenzene. The calculated value of ∆∆Gext (∆∆G = ∆GCs+ − ∆GNa+) is found to be −41.82 kcal/mol with 1,3 alternate‐diethoxy calix[4]arene 3′‐methoxy benzocrown‐6, which is higher than that obtained with calix [4] bis‐crown‐6 (−5.24 kcal/mol). The newly designed ligand might be suitable for the selective extraction of Cs+ over Na+ in the reprocessing of nuclear waste and thus invites experimentalists to test this DFT finding in the laboratory.

中文翻译:

通过杯盖[4] arene-crown-6上的各种取代基进行电子效应的密度泛函理论调整,以有效地进行Cs +​​离子包封和萃取

根据结果​​分析,本文报告了杯[4]芳烃-冠-6(C4C6)和取代的C4C6的Cs +配合物Cs +配合物的结构,能级和量子化学描述符。使用密度泛函理论(DFT)获得。C4C6和1,3交替二乙氧基C4C6中的苯并基取代导致结合能(BE)降低。苯甲基进一步被甲基,甲氧基和氨基取代会导致BE的增加,而硝基取代会导致C4C6的BE降低,而在1,3交替双乙氧基杯[4] arenebenzocrown-6的情况下与其他配合物相比,甲氧基取代导致最高的BE。计算的吉布斯自由能ΔG气体在1,3交替二乙氧基C4C6及其取代的配体的情况下,也遵循与BE相同的顺序。此外,在不同溶剂(甲苯,氯仿,辛醇和硝基苯)中,使用热电循环和类似导体的筛选模型,计算了络合的ΔG。Δ的值ģ EXT被发现与增加的溶剂的介电常数增加,并且被认为是在最高硝基苯。分子分析中的原子揭示了CsO键的部分离子特征。在所有研究的配合物中,1,3交替二乙氧基杯[4]亚芳基3'-甲氧基苯并冠-6在硝基苯中表现出最高的ΔG ext。Δ∆ G的计算值ext(∆∆ G = ∆ G Cs + − ∆ G Na +)与1,3交替-二乙氧基杯[4]芳烃3'-甲氧基苯并冠冕-6相比为−41.82 kcal / mol。杯[4]双冠-6(−5.24 kcal / mol)。新设计的配体可能适用于在核废料的后处理中通过Na +选择性萃取Cs +的方法,因此邀请实验人员在实验室中测试该DFT发现。
更新日期:2020-08-25
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