| Autor: |
Wu K; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, U.K., Ronson TK; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, U.K., Goh L; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, U.K., Xue W; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, U.K., Heard AW; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, U.K.; Astex Pharmaceuticals, 436 Cambridge Science Park, Cambridge CB4 0QA, U.K., Su P; College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong 518055, China., Li X; College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong 518055, China., Vinković M; Astex Pharmaceuticals, 436 Cambridge Science Park, Cambridge CB4 0QA, U.K., Nitschke JR; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, U.K. |
| Abstrakt: |
The allosteric regulation of biomolecules, such as enzymes, enables them to adapt and alter their conformation to fit specific substrates, expressing different functionalities in response to stimuli. Different stimuli can also trigger synthetic coordination cages to change their shape, size, and nuclearity by reconfiguring the dynamic metal-ligand bonds that hold them together. Here we demonstrate an abiological system consisting of different organic subcomponents and Zn II metal ions, which can respond to simple stimuli in complex ways. A Zn II 20 L 12 dodecahedron transforms to give a larger Zn II 30 L 12 icosidodecahedron through subcomponent exchange, as an aldehyde that forms bidentate ligands is displaced in favor of one that forms tridentate ligands together with a penta-amine subcomponent. In the presence of a chiral template guest, the same system that produced the icosidodecahedron instead gives a Zn II 15 L 6 truncated rhombohedral architecture through enantioselective self-assembly. Under specific crystallization conditions, a guest induces a further reconfiguration of either the Zn II 30 L 12 or Zn II 15 L 6 cages to yield an unprecedented Zn II 20 L 8 pseudo-truncated octahedral structure. The transformation network of these cages shows how large synthetic hosts can undergo structural adaptation through the application of chemical stimuli, opening pathways to broader applications. |
