Controlling the extent of spin exchange coupling in 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) biradicals via molecular recognition with cucurbit[n]uril hosts |
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Authors: | Yi Song Captain Burjor Ottaviani M Francesca Kaifer Angel E |
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Institution: | Department of Chemistry and Center for Supramolecular Science, University of Miami, Coral Gables, Florida 33124-0431, United States. |
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Abstract: | The binding interactions between two paramagnetic cobaltocenium guests and the hosts cucurbit7]uril (CB7) and cucurbit8]uril (CB8) were investigated using a combination of electronic absorption, NMR, and electron paramagnetic resonance (EPR) spectroscopies, mass spectrometry, and X-ray crystallography. Guest 1, (4-amido-2,2,6,6-tetramethylpiperidine-1-oxyl)cobaltocenium, forms very stable inclusion complexes with CB7 and CB8. However, CB7 interacts with 1 by including the organometallic cobaltocenium unit, while CB8 engulfs the TEMPO residue. The corresponding equilibrium association constant (K) values are 2.8 ± 0.3 × 10(6) M(-1) for CB7?1 and 2.1 ± 1.0 × 10(8) M(-1) for CB8?1. Biradical guest 2, 1,1'-bis(4-amido-2,2,6,6-tetramethylpiperidine-1-oxyl)cobaltocenium, forms a very stable ternary complex with two CB8 hosts, in which each 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) residue is encircled by a host molecule. The structure of this ternary complex was confirmed in the solid state using single-crystal X-ray diffraction. Binding of the TEMPO side arms by the CB8 hosts gradually decreases the observed level of spin exchange coupling between the two nitroxide groups. In the final 2:1 complex, no spin exchange coupling was observed, but the initial levels of spin exchange coupling could be regenerated in a reversible fashion by adding a competing guest, adamantyltrimethylammonium (AdTMA), to the solution. The binding interactions between 2 and CB7 are similar but the stabilities of the 1:1 and 2:1 complexes are much lower than those of the corresponding CB8 complexes. |
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