Modulation of Charge-transfer Complexes Assisted by Complementary Hydrogen Bonds of Nucleobases: TCNQ Complexes of a Uracil-substituted EDO-TTF
Modulation of Charge-transfer Complexes Assisted by Complementary Hydrogen Bonds of Nucleobases: TCNQ Complexes of a Uracil-substituted EDO-TTF
复制标题
核碱基互补氢键辅助的电荷转移复合物的调节：尿嘧啶取代的 EDO-TTF 的 TCNQ 复合物
作者：
Y. Morita;他4人
合成了一种含正丁基尿嘧啶的氢键功能化乙二氧基四硫富瓦烯(EDO-TTF)衍生物。在晶体结构中，尿嘧啶部分的沃森-克里克型互补氢键形成了一对施主分子，通过S与S的⋯相互作用和四氢呋喃部分的π-堆栈进一步聚集，形成了二维片层。在与四氰基喹甲烷的电荷转移络合物的形成中，结晶条件调节了Watson-Crick和反向Watson-Crick类型的互补氢键对之间的微妙平衡，控制了络合物的化学计量、电离性和分子堆积。通过快速挥发反应溶剂得到了具有Watson-Crick氢键的高导电性混合价络合物，用慢速气相扩散法得到了形成反向Watson-Crick氢键的低导电性中性络合物。
A hydrogen bond functionalized ethylenedioxytetrathiafulvalene (EDO-TTF) derivative having an n-butyluracil moiety was synthesized. In the crystal structure, the Watson–Crick-type complementary hydrogen bonds of the uracil moiety formed a pair of donor molecules, which further aggregated by S⋯S interactions and π-stacks of the TTF moiety to construct a two-dimensional sheet. In the charge-transfer complex formation with tetracyanoquinodimethane, the crystallization conditions modulated the subtle balance between Watson–Crick and reverse Watson–Crick types of complementary hydrogen-bonded pairs, controlling stoichiometry, ionicity and molecular packing of the complexes. A highly conducting mixed valence complex with the Watson–Crick-type hydrogen bonds was yielded by the quick evaporation of reaction solvent, and a low-conducting neutral complex forming reverse Watson–Crick-type hydrogen bonds was obtained by the slow vapor diffusion method.