Tetrathiafulvalene-type Electron Donors Bearing Biimidazole Moieties: MultifunctionalUnits with Hydrogen Bonding Abilities
Tetrathiafulvalene-type Electron Donors Bearing Biimidazole Moieties: MultifunctionalUnits with Hydrogen Bonding Abilities
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带有联咪唑部分的四硫富瓦烯型电子给体：具有氢键能力的多功能单元
DOI：
10.1002/ejoc.201200426
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
Y. Morita
中科院分区：
文献类型：
--
作者：
T. Murata;K. Nakasuji;Y. Morita
设计并合成了以4，4 ′-和2，2 ′-联咪唑单元（分别为1和2）为氢键单元的新型四硫富瓦烯（TTF）给电子体分子.循环伏安法表明，1和2都具有很强的供电子能力，接近TTF，具有两阶段可逆的氧化还原过程。在1的晶体结构中，均匀的π堆叠、TTF部分的并排S···S相互作用以及通过结晶水分子的联咪唑单元的多个氢键有助于形成二维供体层。2的晶体结构由2，2 ′-联咪唑特有的互补氢键和TTF上的S···S相互作用形成的一维条带构成。在2与碘的电荷转移盐中，（I82-）无维梳状结构作为阴离子部分，N-H···I氢键将供体分子锚定在（I82-）n链的空腔中。1和2与四氰基醌二甲烷形成复合物，得到具有半导体性质的混合价电荷转移复合物（室温电导率分别为10- 3和10- 1 S cm-1）。
New tetrathiafulvalene (TTF)‐based electron‐donor molecules having 4,4′‐ and 2,2′‐biimidazole units (1and2, respectively) as hydrogen bonding units were designed and synthesized. Cyclic voltammetry showed that both1and2possess strong electron‐donating abilities close to that of TTF with two‐stage reversible redox processes. In the crystal structure of1, uniform π stacking, side‐by‐side S···S interactions of the TTF moiety, and multiple hydrogen bonds of the biimidazole unit via crystalline water molecules contribute to the formation of a two‐dimensional donor layer. The crystal structure of2was constructed by one‐dimensional ribbons formed by complementary hydrogen bonds characteristic to 2,2′‐biimidazole and side‐by‐side S···S interactions on the TTF moiety. In the charge‐transfer salt of2with iodine, which included the (I82–)none‐dimensional comb‐like structure as the anion part, the N–H···I hydrogen bond anchored the donor molecule in the cavity of the (I82–)nchain. Complex formation of1and2with tetracyanoquinodimethane afforded mixed‐valence charge‐transfer complexes showing semiconducting behaviors (room temperature conductivities = 10–3and 10–1S cm–1, respectively).