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Assembly of nucleobases into rings and cages via metal ions
Published in Journal of Coordination Chemistry, 2022
Bernhard Lippert, Pablo J. Sanz Miguel
An alternative to intramolecular chelation of a metal ion by a nucleotide, which provides the mentioned macrochelate, is intermolecular metal binding, leading to a dinuclear complex. [Pt(en)(5′-CMP)]2 (with 5′-CMP = 5′-cytidine monophosphate) [17] is a typical example. In it, both PtII ions bind to N3 of the cytosine and an oxygen of the phosphate group each, thereby producing a head-tail dinuclear species. There is even the possibility of having exclusive metal binding to two bridging phosphate groups, with the nucleobases not involved in metal binding at all, such as in [Cu(L)(H2O)(5′-UMP)]2 [17] (with L = o-phenanthroline and 5′-UMP = 5′-uridine monophosphate), but of course, this pattern is phosphate—rather than nucleobase—specific. Related to this pattern are dinuclear nucleobase complexes with other bridging ligands such as hydroxide [18] or halide [19], and terminal nucleobases, which we likewise will not discuss further. The more typical 2:2-complexes are those, in which both metal ions cross-link donor sites of the heterocyclic rings. Examples today include virtually all common nucleobases.