Center of Spectroelectrochemistry, Department of Electrochemistry and Conducting Polymers, Leibniz Institute for Solid State and Materials Research, D-01069 Dresden, Germany.
Phys Chem Chem Phys. 2011 Aug 7;13(29):13403-9. doi: 10.1039/c1cp20738e. Epub 2011 Jun 27.
A detailed in situ Electron Spin Resonance (ESR)/UV-Vis-NIR spectroelectrochemical study of the oligothiophene/single walled carbon nanotube (SWCNT) interphase is presented to provide an insight into the interaction of nanotubes with oligothiophenes. Used as electrode materials these composites are followed in situ with respect to the paramagnetic and diamagnetic states formed upon electrochemical charging. The variation of the oligomer chain length and the type, position and number of substituents at the oligomer is used to understand the structural influence on the formation of the charged states in the material upon electrochemical reaction. For β,β'-dihexylsexithiophene (β,β'-DHST)-SWCNT the enlarged current in the composite and a decreased radical cation concentration can be explained by the formation of π-dimers. By interaction with SWCNTs the π-dimerization of oligothiophenes and the formation of multi π-stack structures occur. For α,ω-dicyano-β,β'-dibutylquaterthiophene (DCNDBQT)-SWCNT a new paramagnetic structure of the oligomer is formed as an intermediate which undergoes follow-up reactions. Using different substituted oligothiophenes their interaction with nanotubes can be understood with respect to the structure of the oligomer.
本文对寡聚噻吩/单壁碳纳米管（SWCNT）界面进行了详细的原位电子自旋共振（ESR）/紫外可见近红外光谱电化学研究，旨在深入了解纳米管与寡聚噻吩的相互作用。作为电极材料，这些复合材料在电化学充电过程中形成顺磁和抗磁态时进行原位跟踪。寡聚物链长的变化以及寡聚物上取代基的类型、位置和数量被用来理解结构对电化学反应中材料中带电态形成的影响。对于β,β'-二己基六噻吩（β,β'-DHST）-SWCNT，复合材料中电流增大和自由基阳离子浓度降低可以用π-二聚体的形成来解释。通过与 SWCNT 的相互作用，寡聚噻吩发生π-二聚化并形成多π-堆叠结构。对于α,ω-二氰基-β,β'-二丁基四噻吩（DCNDBQT）-SWCNT，形成了一种新的作为中间体的寡聚物顺磁结构，随后发生后续反应。使用不同取代的寡聚噻吩，可以根据寡聚物的结构来理解它们与纳米管的相互作用。
