beta-Substituted Terthiophene [2]Rotaxanes

Two kinds of beta-substituted terthiophene [2]rotaxanes were synthesized using the host-guest pairs of the electron-deficient cyclophane cyclobis(paraquat-p-phenytene) (CBPQT(4+)) and the electron-rich terthiophenes with diethyleneglycol chains at the beta-position. One is made from the alpha-position non-substituted terthiophene (3T-beta-Rx) and the other is made from the alpha-dibromo-substituted terthiophene (3TBr-beta-Rx). The binding constants of the P-substituted terthiophene threads were confirmed to be smaller than that of the beta-substituted terthiophene analogue. By UV/Vis absorption measurements, we confirmed the charge-transfer (CT) band in the visible region with an extinction coefficient of approximate to 10(2) (M-1 cm(-1)). Strong, but not quantitative, quenching of the terthiophene fluorescence was confirmed for the [2]rotaxanes. Although the beta-substituted terthiophene thread was electrochemically polymerizable, the [2]rotaxane 3T-beta-Rx was not polymerizable. This result indicates that the interlocked CBPQT(4+) macrocycle effectively suppresses the electrochemical polymerization of the terthiophene unit because electrostatic repulsive and steric effects of CBPQT(4+). hinder the dimerization of the terthiophene radical cations. In the electrochemical measurement, we confirmed the shift of the first reduction peak towards less negative potential compared to free CBPQT(4+) and the splitting of the second reduction peak. These electrochemical behaviors are similar to those observed for the highly-constrained [2]rotaxanes. The beta-substituted terthiophene [2]rotaxanes reported herein are important key compounds to prepare polythiophene polyrotaxanes.