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

钌三（2,2′-联吡啶）配合物（Ru(bpy)_3^<2+>）与电活性材料之间的光致电子转移（PIED）从人工光合作用和光能转换的角度进行了广泛的研究。由于Ru(bpy)_3^<2+>可以在适当的牺牲剂存在下再生，因此它可以作为光催化剂。我们已经报道了苯胺和苯胺二聚体，即af -苯基-对苯二胺（PPD）的热聚合，通过照亮由Ru(bpy)_3^<2+>-结合Naflon和甲基紫素(MV^<2+>)-悬空聚硅氧烷组成的双层膜或由Ru(bpy)_3^<2+>-和MV^<2+>-结合Flemion组成的单层膜。粘土矿物具有带阴离子的中间层，并通过阳离子交换在其中间层空间插入带正电的有机分子。因此，我们在酸性水溶液中插入Ru(bpy)_3^<2+>和质子化PPD，并检测了Ru(bpy)_3^<2+>在二维层间空间中的光聚合率。我们发现带阴离子的粘土层既可以作为模板，也可以作为反离子形成酸掺杂的聚苯胺（PAn）导电形式，从而形成具有长共轭的线性导电PAn。考察了其他类型的聚阴离子材料在PPD光催化聚合中的模板效应和酸掺杂效应。聚乙烯基硫酸钾（PVSK）是一种柔性聚阴离子，它提供了PAn/PVSK配合物，该配合物可溶于水或有机溶剂，取决于PPD和PVSK的摩尔比。十二烷基硫酸钠（SDS）是一种形成胶束的阴离子表面活性剂，其胶束表面明显充当粘土中间层的二维模板。另一方面，DNA是一种刚性双螺旋聚阴离子，即使在较低的酸性pH（即pH 3-6）下，也能提供线性酸掺杂的PAn。PPD的吸收带出现圆形二色性，表明PPD分子在DNA提供的局部低pH环境中排列，导致PAn/DNA复合物中形成膨胀线圈PAn。此外，还研究了在Flemion薄膜上的成像以及PAn/DNA/Ru(bpy)_3^<2+>配合物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