Fukumoto Hiroki, Nakajima Hisashi, Kojima Takahiro, Yamamoto Takakazu
College of Biomolecular Functional Engineering, Faculty of Engineering, Ibaraki University, 4-12-1, Nakanarusawa, Hitachi 316-8511, Japan.
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259, Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Materials (Basel). 2014 Mar 11;7(3):2030-2043. doi: 10.3390/ma7032030.
π-Conjugated polymers based on indigo unit were prepared. Dehalogenative polycondensation of -hexyl-6,6'-dibromoindigo with a zerovalent nickel complex gave a homopolymer, , in 77% yield. Copolymer of -hexyl-indigo and pyridine, , was also prepared in 50% yield. showed good solubility in organic solvents, whereas was only soluble in acids such as HCOOH. The weight-average molecular weights () of and were determined to be 10,000 and 40,000, respectively, by a light scattering method. Pd-catalyzed polycondensation between 6,6'-dibromoindigo with -BOC (BOC = -butoxycarbonyl) substituents and a diboronic compound of 9,9-dioctylfluorene afforded the corresponding alternating copolymer, , as a deep red solid in 98% yield. was soluble in -methyl-2-pyrroridone and showed an of 29,000 in GPC analysis. Treatment of with CF₃COOH smoothly led to a BOC-deprotection reaction to give an insoluble deep green polymer, , in a quantitative yield. Diffuse reflectance spectra of powdery and showed peaks at about 580 nm and 630 nm, respectively, which are thought to originate from the indigo unit.
制备了基于靛蓝单元的π共轭聚合物。己基-6,6'-二溴靛蓝与零价镍配合物进行脱卤缩聚反应，以77%的产率得到均聚物。己基靛蓝与吡啶的共聚物也以50%的产率制备得到。表现出在有机溶剂中有良好的溶解性，而仅可溶于诸如HCOOH等酸中。通过光散射法测定和的重均分子量（）分别为10,000和40,000。钯催化6,6'-二溴靛蓝与带有-BOC（BOC = -丁氧羰基）取代基的9,9-二辛基芴的二硼酸化合物之间的缩聚反应，以98%的产率得到相应的交替共聚物，为深红色固体。可溶于N-甲基-2-吡咯烷酮，在凝胶渗透色谱分析中的为29,000。用CF₃COOH处理可顺利导致BOC脱保护反应，以定量产率得到不溶性深绿色聚合物。粉末状和的漫反射光谱分别在约580 nm和630 nm处出现峰，据认为这些峰源自靛蓝单元。
