Abstract

In recent years, luminescent supramolecular coordination complexes (SCCs), including 2D-metallacycles and 3D-metallacages have been utilised for biomolecular analysis. Unlike small-molecular probes, the dimensions, size, shape, and flexibility of these complexes can easily be tuned by combining ligands designed with particular geometries, symmetries and denticity with metal ions with strong geometrical binding preferences. The well-defined cavities that result, in combination with the other non-covalent interactions that can be programmed into the ligand design, facilitate great selectivity towards guest binding. In this Review we will discuss the application of luminescent metallacycles and cages in the binding and detection of a wide range of biomolecules, such as carbohydrates, proteins, amino acids, and biogenic amines. We aim to explore the effect of the structural diversity of SCCs on the extent of biomolecular sensing, expressed in terms of sensitivity, selectivity and detection range.

Highlights

  • In recent years, luminescent supramolecular coordination complexes (SCCs), including 2D-metallacycles and 3D-metallacages have been utilised for biomolecular analysis

  • Discrete metallacycles can provide an efficient platform for energy transfer and light-harvesting, since it is possible to introduce multiple functional moieties into SCCs with precise control over stoichiometry and the position of the individual functional groups.[1b] the known anticancer activity of organometallic ruthenium and platinum complexes has prompted the development of therapeutic SCCs including these metals centres for advanced biomedical applications.[2]

  • Unlike small molecule-based probes, such coordination complexes generally exhibit a ‘turn-on’ or ratiometric response in the presence of biomolecules, as the binding of analytes changes the conformational flexibility of metallacycles or their aggregation-induced emission properties

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Summary

Tuning the photophysical properties of SCCs

The photophysical properties of metallacycles and cages are highly diverse. Even small variations in the ligand design can yield substantial changes to the shape, size or flexibility of the complexes formed, which can in turn lead to changes in their optical properties. She carried out postdoctoral work in the same group until 2013 before joining the Royal Society of Chemistry as an editor. A combination of non-covalent interactions, such as Coulombic attraction, hydrophobic effects, π-π stacking and hydrogen bonding can be engineered into the ligand design to compliment the fixed cavity size and produce hosts with high selectivity towards target analytes Using these means the discrimination of structurally similar analytes, such as mono- and disaccharides can be attained and yield an optical response.[26]. 3. Unlike small molecule-based probes, such coordination complexes generally exhibit a ‘turn-on’ or ratiometric response in the presence of biomolecules, as the binding of analytes changes the conformational flexibility of metallacycles or their aggregation-induced emission properties. Coordination-driven self-assembly enables the formation of complex architectures from relatively simple building blocks, making SCCs synthetically accessible

Effect of the microenvironment on the fluorescence properties of SCCs
Detection of biomolecules using supramolecular coordination complexes
Interaction with biogenic amines
Interaction with carboxylic acids
Interactions with nucleotides
Interactions with amino acids
Interactions with proteins
Interactions with carbohydrates
Interactions with chiral biomolecules
Interactions with volatile organic molecules
Concluding remarks and future directions
Conflict of Interest

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