RESUMEN
Construction of discrete, self-assembled architectures in water has gained significant interest in recent years as a wide range of applications arises from their defined 3D structure. In this review we jointly discuss the efforts of supramolecular chemists and biotechnologists who previously worked independently, to tackle discipline-specific challenges associated with construction of assemblies from synthetic and bio-derived components, respectively. Going forward, a more interdisciplinary research approach will expedite development of complexes with real-world applications that exploit the benefits of compartmentalisation. In support of this, we summarise advances made in the development of discrete, water-soluble assemblies, with particular focus on their current and prospective applications. Areas where understanding and methodologies can be transferred from one sector to the adjacent field are highlighted in anticipation this will yield advances not possible from either field alone.
RESUMEN
Isolating metal-organic cage structures which incorporate more than one distinct ligand has been challenging due to competing pressures from narcissistic and social sorting phenomena. Here we report the first example of exclusive formation of a single tetrahedral product from a reaction mixture containing two different bidentate ligands. Exclusive formation of the tetrahedron, which incorporates one unique metal vertex, relies on a triamine to orientate the heteroditopic ligand. Inclusion of perchlorate counterions during the self-assembly process is also found to be a requirement if social sorting is to be avoided. The C3-symmetric structure is characterised by HR-MS, NMR spectroscopy and X-ray crystallography, and provides proof of principle for use of heteroditopic ligands in classical M4L6 supramolecular structures, opening exciting possibilities for their use in separation, storage and catalysis applications.
RESUMEN
Self-assembly and characterisation of a supramolecular trigonal bipyramidal iron cage containing an [FeIII(µ2-F)6(FeII)3]3+ star motif at its core is reported. The complex can be formed in a one step reaction using an heterotopic ligand that supports site-specific incorporation of iron in three distinct electronic configurations: low-spin FeII, high-spin FeII and high-spin FeIII, with iron(II) tetrafluoroborate as the source of the bridging fluorides. Formation of a µ2-F bridged mixed-valence FeII-FeIII star is unprecedented. The peripheral high-spin FeII centres of the mixed-valence tetranuclear star incorporated in the iron cage are highly anisotropic and engage in F-mediated antiferromagnetic exchange with the central FeIII ion.