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Coordination of lanthanide cations to cucurbituril and supramolecular self-assembly in the absence and presence of polychloridometallate ions

Abstract Compared to isolated, simple Ln3+/Q[6] complexes in the absence of polychloridometallate ions, linear coordination polymers have been assembled from lanthanide cations (Ln3+) and cucurbituril (Q[6]) in the presence of polychloridometallate ions as inorganic structure inducers in HCl solution. X-ray diffraction analysis has revealed that not only [CuCl4]2− anions but also [FeCl2(H2O)4]+ cations can induce the coordination of Ln3+ cations to Q[6] so as to form Ln3+/Q[6]-based tubular coordination polymers. The driving forces are considered to be interaction of the electron-deficient carbon sites of the carbonyl dipoles of Q[n] molecules with the chloride ends of the Md-block−Cl bonds in the [Md-blockClx]n− anions or [Md-blockClx]m+ cations, as well as unusual hydrogen bonding between the methine and methylene groups on the back of adjacent Q[n] molecules and the chlorine atoms of the [Md-blockClx]n− ions. We have classified such interactions as ‘back-interaction of Q[n]s’.