期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 111, 期 28, 页码 8020-8026出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp071614u
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Chemical and electrochemical oxidation (or p-doping) of three types of pi-conjugated co-oligomers, Py-Th-(Th)(n)-Th-Py (Py = pyridine unit; Th = thiophene unit; 5a, n = 1; 6a, n = 2), Th-Py-(Th)(n)-Py-Th (5b: n = 1; 6b: n = 2), and Pym-Th-(Th)(n)-Th-Pym (Pym = pyrimidine unit; 5c: n = 1; 6c: n = 2), in solution systems has been studied. The chemical oxidation with NOBF4 proceeded with isosbestic points in the UV-vis spectrum. The UV-vis absorption peak of 5a at 418 nm in CH2Cl2 shifted to 456 nm after oxidation of 5a with NOBF4. The oxidized 5a was easily reduced by N2H4 to give the original UV-vis spectrum of 5a, and 5b, 6b, and 5c behaved similarly in the oxidation and reduction. In the oxidation by NOBF4, an (oxidized co-oligomer)/(original neutral co-oligomer) ratio of 1 was attained at [NOBF4] = 1.3 x 10(-6), 4 x 10(-6), 7 x 10(-6), and 9 x 10(-6) M for 5a, 6b, 5b, and 5c, respectively. The obtained data are considered to reflect the ease of oxidation of the co-oligomer, which is affected by the electron-accepting nature of the N-containing aromatic unit in the co-oligomer and effective pi-conjugated length of the co-oligomer. The cyclic voltammogram of 5a showed three redox couples with anodic peak current potentials of E-pa = 0.75, 1.10, and 1.34 V versus Ag+/Ag, respectively. The first oxidation peak was assigned to one-electron oxidation of 5a, and electronic current of the first anodic peak (i) of 5a and 5c was proportional to (scanning rate)(1/2). From the i- (scanning rate)(1/2) relationship, diffusion constants, D's, of 5a and 5c were estimated to be 9.6 x 10(-6) and 1.7 x 10(-5) cm(2) s(-1), respectively. CV data of 5b with the terminal thiophene units indicated occurrence of electrochemical oxidative polymerization of 5b.
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