Translational dynamics of a non-degenerate molecular shuttle imbedded in a zirconium metal–organic framework |
| |
Authors: | Benjamin H Wilson Louae M Abdulla Robert W Schurko Stephen J Loeb |
| |
Institution: | Department of Chemistry and Biochemistry, University of Windsor, Windsor Ontario N9B 3P4 Canada.; Department of Chemistry and Biochemistry, Florida State University, Tallahassee FL 32306 USA ; National High Magnetic Field Laboratory, Tallahassee FL 32310 USA |
| |
Abstract: | A new 2]rotaxane molecular shuttle linker based on the binding of a 24-crown-8 ether macrocycle at a benzimidazole recognition site was synthesised. The shuttling dynamics of the linker were studied in solution and the structure confirmed by X-ray crystallography. A multivariate Zr(iv) MOF, UWDM-11, containing the new MIM linker and primary linker tetramethylterphenyldicarboxylate was synthesised and the translational motion of the molecular shuttle studied in the solid state. The use of a 13C enriched MIM linker allowed the dynamics of both activated and mesitylene-solvated UWDM-11 to be elucidated by VT 13C CPMAS SSNMR. The incorporation of mesitylene into the pores of UWDM-11 resulted in a significant increase in the barrier for thermally driven translation of the macrocycle.An unsymmetrical molecular shuttle was incorporated into the octahedral cavities of a Zr(iv) MOF. 13C SSNMR showed that the presence of mesitylene in the pores results in an increase in the barriers for the thermally driven motion of the macrocycle. |
| |
Keywords: | |
|
|