13C NMR Longitudinal Relaxation Time Studies of a Molecular Tweezers Derived from a Calixarene-Porphyrin Conjugate

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Zn(II)porphyrin-substituted calix[4]arene 1 serves as molecular tweezers for 1,4-diazabicyclo[2.2.2] octane (DABCO) selectively, which led to the formation of Ensemble I. The molecular segments composing the calixarene cavity change upon inclusion of DABCO as Ensemble I were evaluated through 13C NMR longitudinal relaxation times (T1) for the first time. As for Enemble I, the 1:1 complex should be formed. The T1 values for Ensemble I are generally smaller than those for 1: in CDCl2CDCl2, DT1 = 5.03 s for C-1, 5.31 s for C-2, 0.13 s for C-3, 0.7 s for C-4, and 0.16 s for C-5. This substantiates that the rings of Ensemble I are firmly freezed because of the two-point coordination by DABCO. In 1, the T1 values for C-3 are always greater than those for C-4, and the difference between C-3 and C-4 is slight. As for Ensemble I, on the other hand, the difference between C-3 and C-4 is large. We can suggest two different motions for phenol units in 1 and Ensemble I: a rotational motion around a C-1 to C-4 axis (A) and a seesaw motion around a C-2 to C-2’ axis (B). The data indicate that in Ensemble I motion (A) is predominant over motion (B). This indicates that motion (B) is specifically suppressed because of the two-point coordination interactions in Ensemble I.
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