- Research Article
- 10.5937/kgjsci2503069c
Quadratic acid as a structural motive in a Lehn-type cryptand - prediction of ion selectivity by quantum chemical calculations. XX
- Jan 01, 2025
- Kragujevac Journal of Science
- Thomas Capponi + 5 more +5
The ion selectivity of [2 Qua.2 Qua.2 Qua] was investigated based on descriptors derived from quantum chemical calculations (B3LYP/LANL2DZp), including structural aspects and model reaction energies. The results clearly show that the cryptand [2 Qua.2 Qua.2 Qua] demonstrates the same ion selectivity as the earlier investigated cryptands [2 Oxa.2 Oxa.2 Oxa] and [2.2.2]. There is a clear preference for K<sup>+</sup> (over Rb<sup>+</sup>) and Ba<sup>2+</sup> (over Sr<sup>2+</sup>). The substitution of the oxalic acid or ethyl moieties by the quadratic acid block, with its sp<sup>2</sup>-carbon cycle, makes the cryptates [M ⸦ 2 Qua.2 Qua.2 Qua]<sub>m+</sub> less flexible in comparison to [M ⸦ 2 Oxa.2 Oxa.2 Oxa]<sub>m+</sub> and [M ⸦ 2.2.2]<sub>m+</sub>. To compensate for the quadratic acid-based inflexibility, the cryptand [2 Qua.2 Qua.2 Qua] utilizes twisting the CN⸱⸱⸱NC angle to improve the coordination of guest cations and nest them in a better way in [2 Qua.2 Qua.2 Qua].
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