期刊
CHEMISTRY-SWITZERLAND
卷 3, 期 4, 页码 1203-1214出版社
MDPI
DOI: 10.3390/chemistry3040088
关键词
coordination cage; crystal structure; host-guest chemistry
资金
- Leverhulme Trust [RPG-2019-149]
- European Union [765297]
- EPSRC [EP/R03382X/1]
- University ofWarwick
- Marie Curie Actions (MSCA) [765297] Funding Source: Marie Curie Actions (MSCA)
- EPSRC [EP/R03382X/1] Funding Source: UKRI
New synthetic routes are used to introduce various substituents into a M8L12 cubic coordination cage, allowing the formation of functionalized cage cores with metal ions. This allows for a diverse range of synthetic opportunities and increased solubility of the cages.
New synthetic routes are presented to derivatives of a (known) M8L12 cubic coordination cage in which a range of different substituents are attached at the C-4 position of the pyridyl rings at either end of the bis(pyrazolyl-pyridine) bridging ligands. The substituents are (i) -CN groups (new ligand L-CN), (ii) -CH2OCH2-CCH (containing a terminal alkyne) groups (new ligand L(C)); and (iii) -(CH2OCH2)(3)CH2OMe (tri-ethyleneglycol monomethyl ether) groups (new ligand L-PEG). The resulting functionalised ligands combine with M2+ ions (particularly Co2+, Ni2+, Cd2+) to give isostructural [M8L12](16+) cage cores bearing 24 external functional groups; the cages based on L-CN (with M2+ = Cd2+) and L(C) (with M2+ = Ni2+) 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 -(CH2OCH2)(3)CH2OMe 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.
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