'Click' to functionalise: Synthesis, characterisation and enhancement of the physical properties of a series of exo- and endo-functionalised Pd ₂L₄ nanocages

The synthesis of self-assembled metallosupramolecular architectures has been of steadily growing interest in recent years due to their diverse applications. Appending additional functionality to the ligands of these architectures has been limited as this often involves incorporation of coordinating groups that can potentially disrupt formation of the desired structure. Herein we report the use of the facile, functional group tolerant and high yielding CuAAC 'click' reaction to attach a variety of functional moieties to a tripyridyl ligand system. Despite the presence of the potentially coordinating 1,2,3-triazole rings, self-assembly of quadruply-stranded dipalladium(ii) cage architectures in the presence of Pd(ii) ions was almost universally observed for the functionalised "click" ligands. The only system which did not assemble into the expected cage featured a 2-(1,2,3-triazol-4-yl)pyridine binding pocket which sequestered the Pd(ii) ions. Blocking this chelating pocket with an inert [Re(CO)₃Cl] moiety restored the ability of the ligand to self-assemble into the desired quadruply-stranded dipalladium(ii) cage, generating a heterometallic cage architecture. All ligands and cage architectures have been characterised using ¹H, ¹³C and DOSY NMR, IR, UV-Vis and emission spectroscopies, mass spectrometry and in some cases by X-ray crystallography. Whilst the parent cage system is devoid of useful physical properties and displays a limited range of solubility, the CuAAC methodology provides a facile method to enhance the cage's properties. A variety of fluorescent, redox active and biologically relevant species have been appended to the external surface of these cages. These groups enabled the generation of a series of aqueous soluble, fluorescent and electrochemically active Pd₂L₄ cages in a modular fashion.