PHOTOPOLYMERIZATION OF ANILINE DIMER IN CLAY INTERLAYERS AND CHARACTERIZATION OF RESULTING POLYANILINE/CLAY COMPOSITES

从人工光合作用和光能转化的角度出发，对钌-三（2，2 '-联吡啶）配合物（Ru（bpy）_3 ^<2 +>）与电活性材料之间的光诱导电子转移（PIED）进行了广泛的研究。由于Ru（bpy）_3 ^<2 +>在适当的牺牲剂存在下可以再生，因此它起着光催化剂的作用。我们已经报道了苯胺和苯胺二聚体（即AF-苯基-对苯二胺（PPD））的光聚合，通过照射由Ru（bpy）_3 ^<2 +>-掺入的Naflon和甲基紫精（MV ^<2 +>）-侧基聚硅氧烷组成的双层膜或由Ru（bpy）_3 ^<2 +>-和MV ^<2 +>-掺入的Flemion组成的单层膜。粘土矿物具有带阴离子电荷的夹层，并且通过阳离子交换在其夹层空间中插入带正电荷的有机分子。因此，我们将Ru（bpy）_3 ^<2 +>和质子化的PPD插入锂蒙脱石粘土中，即，Ionite H（INT）在酸性水溶液中的光聚合反应 关于我们 在二维层间空间中，Ru（bpy）_3 ^<2 +>对PPD的吸附作用。研究发现，阴离子型粘土层不仅作为模板剂，而且作为反离子，形成了具有长共轭的导电聚苯胺（PAn），并考察了其它类型的聚阴离子材料在PPD光催化聚合中的模板和酸掺杂效应。聚乙烯基硫酸钾（PVSK）是一种柔性的聚阴离子，它与聚苯胺（PAn）形成了一种配合物，该配合物可溶于水或有机溶剂，其溶度取决于PPD与PVSK的摩尔比。十二烷基硫酸钠（SDS），胶束形成的阴离子表面活性剂，得到了一个复杂的类似INT，胶束表面显然作为一个二维模板作为粘土夹层。另一方面，DNA，一种刚性双螺旋聚阴离子，即使在酸性较低的pH下也能得到线性酸掺杂的PAn，即，pH值3 - 6。PPD吸收带中圆二色性的出现表明PPD分子在DNA提供的局部较低pH环境中排列，导致PAn/DNA复合物中形成扩展卷曲PAn。此外，还考察了PAn/DNA/Ru（bpy）_3 ^<2 +>配合物在Flemion膜上的成像以及作为发光二极管的应用。少

Photoinduced electron transfer (PIED between ruthenium tris(2 ,2'-bipyridyl) complex (Ru(bpy)_3^<2+>) and electroactlve materials has been studied extensively from the stand point of artificial photosynthesis and photoenergy conversion. Since Ru(bpy)_3^<2+> can be regenerated in the presence of appropriate sacrificial agents, it acts as a photocatalyst. We have already reported hotopolymerization of aniline and an aniline dimer, i.e. , AF-phenyl-p-phenylenediamine (PPD), by illuminating a bilayer film composed of Ru(bpy)_3^<2+>-incorporated Naflon and methylviologen (MV^<2+>)-pendant poly(siloxane) or a single layer film composed of Ru(bpy)_3^<2+>- and MV^<2+>-incorporated Flemion. Clay minerals have anionically-charged interlayers and intercalate, by cation exchange, positively-charged organic molecules in their interlayer spaces. We thus intercalated Ru(bpy)_3^<2+> and protonated PPD in a hectorite clay, i.e., Ionite H (INT), in acidic aqueous solution and examined photopolymerizatio … More n of PPD by Ru(bpy)_3^<2+> in the two-dimensional interlayer spaces. We found that the anionically-charged clay layers act as templates and also as counter ions for the acid-doped conducting form of polyaniline(PAn) formed, giving linear conductive PAn with long conjugation.The template and acid-doping effects of other types of polyanionic materials in photocatalytic polymerization of PPD were also examined. Potasium polyvinylsulfate (PVSK), a flexible polyanion, afforded a PAn/PVSK complex which is soluble either in water or in an organic solvent, depending upon the molar ratio of PPD and PVSK. Sodium dodecyl sulfate (SDS), a micelle-forming anionic surfactant, gave a complex similar to that given by INT, the micellar surface apparently acting as a two-dimensional template as the clay interlayer. DNA, a rigid double-helical polyanion, on the other hand, afforded a linear acid-doped PAn even at less acidic pH, i.e.,pH 3-6. Emergence of circular dichroism in the absorption band of PPD suggests alignment of PPD molecules in the local lower pH environment provided by DNA, leading to formation of expanded-coil PAn in the PAn/DNA complex. Additionally, image formation on the Flemion film as well as application of a PAn/DNA/Ru(bpy)_3^<2+> complex as a light emitting diode was also examined. Less