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换的角度出发，研究了三(2，2‘-联吡啶)Ru(Bpy)_3和电活性材料之间的光致电子转移。由于在适当的牺牲剂存在下，Ru(Bpy)_3^&lt；2&gt；可以再生，因此它起到光催化剂的作用。我们已经报道了苯胺和苯二胺二聚体(PPD)的光聚合反应。这种聚合反应是由Ru(Bpy)_3^&lt；2&gt；-Naflon和甲基紫精(MV^&lt；2&gt；)组成的双层膜或由Ru(Bpy)_3^&lt；2&gt；-和MV^&lt；2&gt；-Flemion组成的单层膜。粘土矿物具有带阴离子的夹层，并通过阳离子交换将带正电荷的有机分子插入其夹层空间。因此，我们在酸性水溶液中插层Ru(Bpy)_3和质子化的PPd，即离子H(INT)，并考察了光聚合…在二维层间空间中，Ru(Bpy)3^和lt；2&gt；对PPD的影响较大。研究发现，阴离子粘土层既可以作为模板，也可以作为聚苯胺(PAN)酸掺杂导电形式的反离子，得到长共轭的线型导电PAN。同时考察了其他类型聚阴离子材料在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)是一种柔性的聚阴离子，它提供了一种PAN/PVSK络合物，该络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(十二烷基硫酸钠)是一种形成胶束的阴离子表面活性剂，它提供了一种类似于INT的络合物，胶束表面明显充当了粘土夹层的二维模板。另一方面，DNA是一种刚性的双螺旋聚阴离子，即使在酸性较弱的pH，即pH 3-6的情况下，也能提供线性的酸掺杂PAN。在PPD的吸收带中出现圆二色谱，表明PPD分子在DNA提供的局部低pH环境中排列，导致PAN/DNA复合体中形成扩展的盘状PAN。此外，还研究了聚苯胺/DNA/Ru(Bpy)_3~(2&gt；)络合物在荧光薄膜上的成象及其作为发光二极管的应用。较少

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