Abstract
It has been shown experimentally that theCa2+/Ba2+ potentiometric selectivity ofphosphoryl-containing podandR–-O–-(CH2–-CH2–-O)nndash;-R,R = –-C6H4–-P(O)Ph2, n = 3 (I),switches to Ba2+/Ca2+ when the ligand containsthe longer polyether chain, n = 5 (II). Here, we reportmolecular dynamics and free energy perturbation simulationsperformed using the amber 4.1 program on the complexesL.M2+ (M2+ = Ca2+, Sr2+ andBa2+, L = I and II) in the gas phase inorder to gain a microscopic insight into structural and energy bindingproperties of podands as a function of n. Mixed QM/MM (PM3/ amber) calculations were performed toanalyse the role of polarisation effects on the complexation selectivityof podands. It isshown that an increase of n does not affect the interactions ofM2+ with phosphine oxide groups,but leads to less efficient interactions of small cations with the polyether chain. Calculatedpotentiometric selectivities of I (Ca2+ > Ba2+)and II (Ba2+ > Ca2+) are in agreement with the experimental data.
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