Synthesis and characterization of three novel perfluoro-oligothiophenes ranging in length from the trimer to the pentamer

被引:17
作者
Osuna, RM
Ortiz, RP
Delgado, MCR
Sakamoto, Y
Suzuki, T
Hernández, V
Navarrete, JTL [1 ]
机构
[1] Univ Malaga, Dept Phys Chem, E-29071 Malaga, Spain
[2] Inst Mol Sci, Okazaki, Aichi 4448585, Japan
关键词
D O I
10.1021/jp054205b
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In this Article, we report on the synthesis and full characterization of three perfluorinated oligothiophenes, ranging in length from the trimer to the pentamer (PF-nT, with n = 3, 4, or 5). The differential pulse voltammetry (DPV) analysis of the compounds showed that they can be both oxidized and reduced (i.e., they display a dual or amphoteric electrochemical behavior), with the reduction peaks positively shifted relative to those of the corresponding unsubstituted oligothiophenes. The electrochemically determined energy gaps are in agreement with those measured from the UV-vis-NIR absorption spectra in solution. The conjugational properties have been investigated by means of FT-Raman spectroscopy, both as pure solids and as dilute solutes in CH2Cl2, revealing that: (i) pi-conjugation does not still reach saturation with chain length for the longest oligomer, and (ii) conformational distortions from a nearly coplanar arrangement of the successive thiophene units upon solution are not too large. DFT and TDDFT quantum chemical calculations have been performed, at the B3LYP/6-31G** level, to assess information about the optimized molecular structure, equilibrium atomic charges distribution, energies and topologies of the frontier molecular orbitals (MO) around the gap, vibrational normal modes associated with the most outstanding Raman scatterings, and vertical one-electron excitations that give rise to the main optical absorptions.
引用
收藏
页码:20737 / 20745
页数:9
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