Metal–carboxylato–nucleobase systems: From supramolecular assemblies to 3D porous materials

•MII/carboxylato/nucleobase system: from discrete assemblies to 3D porous materials.•Metal-biomolecule frameworks (MBioFs) based on paddle-wheel shaped SBUs.•Supramolecular metal-biomolecule frameworks based on pairing interactions.•Variability on coordination modes and tautomerism.•Adsorption and magnetic properties.

A complete overview of the preparation of metal–carboxylato–nucleobase architectures that range from supramolecular assemblies to 3D porous materials is reported. The basic building units of these materials consist of metal–nucleobase fragments which link together through coordination bonding or by means of supramolecular assembling among the nucleobases anchored to metal centres. In the case of extended systems based on coordination bonds, the connectivity among the metal centres can be achieved through bridging nucleobases and/or by auxiliary organic linkers such as carboxylate and dicarboxylate anions. The latter bridging mode confers to the nucleobases a greater capacity to involve in molecular recognition processes with other biologically relevant species by means of the establishment of non-covalent interactions such as hydrogen bonding and/or π–π stacking among aromatic groups. On the other hand, the geometrical rigidity imposed by several metal–nucleobase fragments and the base pairing interactions through complementary hydrogen bonding, lead to structural restraints that preclude an effective filling of the space, and as a consequence, it favours the growth of tailor-made open-frameworks based either on coordination bonds (MBioFs) or on non-covalent interactions (supraMBioFs).

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