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首页> 外文期刊>Chemistry: A European journal >Effects of strctural factors on the #pi#-dimerization and/or disproportionation of the cation radical of extended ttf containing thiophene-based #pi#-conjugated spacers
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Effects of strctural factors on the #pi#-dimerization and/or disproportionation of the cation radical of extended ttf containing thiophene-based #pi#-conjugated spacers

机译：结构因素对扩展的含噻吩的＃pi＃共轭间隔基的ttf的阳离子＃pi＃二聚和/或歧化的影响

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摘要

The electrochemical and chemical oxidation of extended TTF 4 and 5 are analsed by cyclic votlammetry,Visible/NIR and ESR spectroscopies, and the X-ray structures of the new salts 5.BF_4(CH_2Cl_2) and 4.ClO_4(THF)_(1/2) are presented.The effects of strucural factors on the #pi#-dimerization or the disproportionation reaction ofthe cation racical are shown.The oxidation of compounnd 4 presents tha successive formation of stable cation radical and dication species both in dichloromethane(DCM) and in a CH_3CN/THF mixtures.In contrast,for compound 5,the stability of the oxidation states strongly depends on the nature of the solvent.In DCM,the oxidation of 5 proceeds by two close one-electron transfers while in CH_3CN/THF the dication is directly formedvia a two-electron process.The X-ray structures ofthe two salts reveal the formation of #pi#-dimers of cation radical.While the dimer (5_2)~(2+) isdue mainly to #pi0#-#pi#interactions between the conjugating spacer,the multiplication of the sulfur atoms in compound 4 contributes to stabilize the dimer by the combined effects of S-S and #pi#-#pi# interactions.Visible/NR and ESR experiments confirm the higher tendency of 4~(+.) to dimerize with the occurrence of dimer and monomer in solution,while for 5~(+.) only the monomer is detected in DCM.Onthe other hand,by dissolution of 5.BF_4(CH_2Cl_2) in CH_3CN,only the neutral and the dicationic states ofcompounds 5 are observed owing to the disproportionation reaction.
机译：扩展的TTF 4和5的电化学和化学氧化通过循环伏安法，可见光/ NIR和ESR光谱分析，以及新盐5.BF_4（CH_2Cl_2）和4.ClO_4（THF）_（1的X射线结构）进行分析。给出了/ 2）。显示了结构因素对阳离子pirac的＃pi＃-二聚或歧化反应的影响。化合物4的氧化表明在二氯甲烷（DCM）中连续形成了稳定的阳离子基团和阳离子种相比之下，对于化合物5，氧化态的稳定性很大程度上取决于溶剂的性质。在DCM中，5的氧化通过两个紧密的单电子转移进行，而在CH_3CN / THF中指示是通过两电子过程直接形成的。两种盐的X射线结构揭示了阳离子基团的＃pi＃-二聚体的形成。而二聚体（5_2）〜（2+）主要是由于＃pi0＃- ＃pi＃共轭间隔基之间的相互作用，su的乘法化合物4中的lfur原子通过SS和#pi＃-＃pi＃相互作用的共同作用而有助于稳定二聚体。可见/ NR和ESR实验证实4〜（+。）随二聚体的出现具有更高的二聚化趋势。溶液中的单体，而对于5〜（+。），则仅在DCM中检测到单体。另一方面，通过将5.BF_4（CH_2Cl_2）溶解在CH_3CN中，仅观察到化合物5的中性和指示性状态。歧化反应。

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