Bipyridinium Polymers That Dock Tetrathiafulvalene Guests in Water Driven by Donor-Acceptor and Ion Pair Interactions
作者:Yun-Chang Zhang、Ying Qin、Hui Wang、Dan-Wei Zhang、Guanyu Yang、Zhan-Ting Li
DOI:10.1002/asia.201600017
日期:2016.4.5
absorption, 1H NMR spectroscopy, and cyclic voltammetry experiments support that in water the BIPY2+ units in the polymers form stable 1:1 charge‐transfer complexes with tetrathiafulvalene (TTF) guests that bear two or four carboxylate groups. These charge‐transfer complexes are stabilized by the donor–acceptor interaction between electron‐rich TTF and electron‐deficient BIPY2+ units and electrostatic attraction
制备了两种水溶性的对亚二甲苯基连接的4,4'-联吡啶(BIPY 2+)聚合物。UV-Vis吸收,1 H NMR光谱和循环伏安法实验证明,聚合物中的BIPY 2+单元与带有两个或四个羧基的四硫富富瓦烯(TTF)客体形成稳定的1:1电荷转移络合物。这些电荷转移复合物通过富电子TTF和缺电子联吡啶之间的供体-受体相互作用稳定2+的二价阳离子联吡啶之间的单位和静电吸引2+单元和连接到TTF核心的阴离子羧酸盐基团。根据UV-Vis实验,在水中估计了混合物的TTF⋅BIPY2 +配合物的表观缔合常数的下限1.8×10 6 m -1。对照实验表明,中性TTF二羧酸和四羧酸与BIPY 2+分子和聚合物的结合能力大大降低。此外,由聚合物的BIPY 2+单元形成的电荷转移配合物的稳定性明显高于两个单体BIPY 2+之间形成的配合物的稳定性。对照和二羧酸TTF供体;这已被归因于联吡啶的相互加强缺电子的性质2+