A Family of Externally-Functionalised Coordination Cages

oleh: Garrett D. Jackson, Max B. Tipping, Christopher G. P. Taylor, Jerico R. Piper, Callum Pritchard, Cristina Mozaceanu, Michael D. Ward

Format: Article
Diterbitkan: MDPI AG 2021-10-01

Deskripsi

New synthetic routes are presented to derivatives of a (known) M<sub>8</sub>L<sub>12</sub> cubic coordination cage in which a range of different substituents are attached at the C<sup>4</sup> position of the pyridyl rings at either end of the bis(pyrazolyl-pyridine) bridging ligands. The substituents are (i) –CN groups (new ligand L<sup>CN</sup>), (ii) –CH<sub>2</sub>OCH<sub>2</sub>–CCH (containing a terminal alkyne) groups (new ligand L<sup>CC</sup>); and (iii) –(CH<sub>2</sub>OCH<sub>2</sub>)<sub>3</sub>CH<sub>2</sub>OMe (tri-ethyleneglycol monomethyl ether) groups (new ligand L<sup>PEG</sup>). The resulting functionalised ligands combine with M<sup>2+</sup> ions (particularly Co<sup>2+</sup>, Ni<sup>2+</sup>, Cd<sup>2+</sup>) to give isostructural [M<sub>8</sub>L<sub>12</sub>]<sup>16+</sup> cage cores bearing 24 external functional groups; the cages based on L<sup>CN</sup> (with M<sup>2+</sup> = Cd<sup>2+</sup>) and L<sup>CC</sup> (with M<sup>2+</sup> = Ni<sup>2+</sup>) have been crystallographically characterised. The value of these is twofold: (i) exterior nitrile or alkene substituents can provide a basis for further synthetic opportunities via ‘Click’ reactions allowing in principle a diverse range of functionalisation of the cage exterior surface; (ii) the exterior –(CH<sub>2</sub>OCH<sub>2</sub>)<sub>3</sub>CH<sub>2</sub>OMe groups substantially increase cage solubility in both water and in organic solvents, allowing binding constants of cavity-binding guests to be measured under an increased range of conditions.