Self-assembled metallosupramolecular architectures have become an increasingly popular area of inorganic chemistry. These systems show a range interesting biological, electronic and photophysical properties. Additionally, they display extensive host-guest chemistry that could potentially be exploited for drug delivery and catalysis. To fully realise these types of applications the ability to generate more functionalised metallosupramolecular architectures is required. In this perspective review we examine the exploitation of 1,2,3-triazole ligands, generated using the Cu(i)-catalysed 1,3-cycloaddition of organic azides with terminal alkynes (the CuAAC "click" reaction), for the assembly of discrete functional metallosupramolecular architectures. These "click" ligands have been used to generate metallomacrocycles, cages and helicates. Some of the architectures have shown promise as anti-cancer and anti-bacterial agents while others have been exploited for small molecule activation and catalysis.
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Angew Chem Int Ed Engl
November 2024
Research School of Chemistry, Australian National University, 2601, Canberra, ACT, Australia.
Current synthetic methods towards Pt(II) lantern-shaped cages involve the use of dry solvent, inert atmosphere, lengthy reaction times, and highly variable yields if isolated. Starting materials such as [Pt(CHCN)](BF) suffer from a poor shelf-life, reducing the synthetic accessibility of various Pt(II) architectures. A new Pt(II) source (with varied counterions), [Pt(3-ClPy)](X) (3-ClPy=3-chloropyridine, X=BF , OTf, NO ), is developed and characterised, showing greatly enhanced shelf-life characteristics under ambient atmospheric conditions.
View Article and Find Full Text PDFChemistry
November 2024
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong, 518060, China.
Numerous metallo-supramolecules with well-defined sizes and shapes have been successfully constructed via the strong coordination interaction between terpyridine (TPY) moieties and ruthenium cations. However, the pseudo-octahedral geometry of
Chemistry
January 2025
School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK.
Heteroleptic (mixed-ligand) coordination cages are of interest as host systems with more structurally and functionally complex cavities than homoleptic architectures. The design of heteroleptic cages, however, is far from trivial. In this work, we experimentally probed the self-assembly of Pd(II) ions with binary ligand combinations in a combinatorial fashion to search for new cis-PdLL' heteroleptic cages.
View Article and Find Full Text PDFDalton Trans
September 2024
School of Chemical Sciences, University of Auckland, 23 Symonds Street, Auckland 1010, New Zealand.
Metallosupramolecular architectures formed from metal ions and bridging ligands are increasing in popularity due to their range of applications and ease of self-assembly. Many are able to readily change their shape and/or function in response to an external stimulus and have the ability to encapsulate guest molecules within their internal cavities. Ferrocenyl groups (Fc) have been incorporated previously within the bridging ligands of metallosupramolecular structures due to their ideal attributes brought about by the structural and rotational flexiblity of the two cyclopentadienyl (Cp) rings coordinated to the Fe(II) centre.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemistry and Biochemistry, University of California, La Jolla, 92092, San Diego, California, United States.
Multivalency is a fundamental principle in nature that leads to high-affinity intermolecular recognition through multiple cooperative interactions that overcome the weak binding of individual constituents. For example, multivalency plays a critical role in lectin-carbohydrate interactions that participate in many essential biological processes. Designing high-affinity multivalent glycoconjugates that engage lectins results in systems with the potential to disrupt these biological processes, offering promising applications in therapeutic design and bioengineering.
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