Spontaneous Assembly of an Organic–Inorganic Nucleic Acid Z‐DNA Double‐Helix Structure

Herein, we report a hybrid polyoxometalate organic–inorganic compound, Na(2)[(HGMP)(2)Mo(5)O(15)]⋅7 H(2)O (1; where GMP=guanosine monophosphate), which spontaneously assembles into a structure with dimensions that are strikingly similar to those of the naturally occurring left‐handed Z‐form of DNA. The helical parameters in the crystal structure of the new compound, such as rise per turn and helical twist per dimer, are nearly identical to this DNA conformation, allowing a close comparison of the two structures. Solution circular dichroism studies show that compound 1 also forms extended secondary structures in solution. Gel electrophoresis studies demonstrate the formation of non‐covalent adducts with natural plasmids. Thus we show a route by which simple hybrid inorganic–organic monomers, such as compound 1, can spontaneously assemble into a double helix without the need for a covalently connected linear sequence of nucleic acid base pairs.