Novel fused D-A dyad and A-D-A triad incorporating tetrathiafulvalene and p-benzoquinone
Novel fused D-A dyad and A-D-A triad incorporating tetrathiafulvalene and p-benzoquinone
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DOI：
10.1021/jo035689f
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发表时间：
2004-03-19
影响因子：
3.6
通讯作者：
Rovira, C
中科院分区：
文献类型：
--
作者：
Dumur, F;Gautier, N;Rovira, C
合成了新型融合的供体-受体二元组（TTF-Q或D-A）和受体-供体-受体三元组（Q-TTF-Q或A-D-A），其中包含供体四硫富瓦烯（TTF）和受体对苯醌（Q）。这些分子的溶液紫外可见光谱显示出低能量吸收带，该吸收带归因于两个拮抗单元之间的分子内电荷转移。循环伏安法显示供体和受体部分存在可逆氧化波和还原波，与TTF/醌单位的比率一致。通过光学和ESR光谱监测分别通过（电）化学氧化和还原获得的这些化合物的阳离子自由基和阴离子自由基的连续产生。阴离子自由基Q-TTF-Q-(.)三联体被证明是II类混合价体系，存在温度依赖性分子内电子转移。还讨论了这些稠合系统在交替 A-D-A 单元的混合堆叠中重叠的晶体学趋势。
Novel fused donor-acceptor dyad (TTF-Q or D-A) and acceptor-donor-acceptor triad (Q-TTF-Q or A-D-A) incorporating the donor tetrathiafulvalene (TTF) and the acceptor p-benzoquinone (Q) have been synthesized. The solution UV-vis spectra of these molecules display a low-energy absorption band that is attributed to an intramolecular charge transfer between both antagonistic units. The presence of reversible oxidation and reduction waves for the donor and acceptor moieties was shown by cyclic voltammetry, in agreement with the ratio TTF/quinone(s) units. The successive generation from these compounds of the cation radical and anion radical obtained upon (electro)chemical oxidation and reduction, respectively, was monitored by optical and ESR spectroscopies. The anion radical Q-TTF-Q-(.)triad was demonstrated to be a class II mixed-valence system with the existence of a temperature-dependent intramolecular electron transfer. The crystallographic tendency of these fused systems to overlap in mixed stacks of alternating A-D-A units is also discussed.