Department of Chemical Science and Engineering, Graduate School of Materials and Chemical Technology Tokyo Institute of Technology, Nagatsuta-cho 4259-G1-9, Midori-ku, Yokohama, 226-8502, Japan.
Macromol Rapid Commun. 2019 Jul;40(14):e1800929. doi: 10.1002/marc.201800929. Epub 2019 May 31.
The synthesis of stannole-2,5-diyl-containing π-conjugated polymers by the post-element transformation of a regioregular organotitanium polymer is described. For example, a 1,1-diphenylstannole-containing polymer is obtained in 83% yield by the reaction of a regioregular organotitanium polymer, which is prepared from 1,4-bis(2-ethylhexyloxy)-2,5-diethynylbenzene and a low-valent titanium complex with diphenyltin dichloride at -50 °C to ambient temperature. The number-average molecular weight and molecular weight distribution (M and M /M ) of the stannole-containing polymer are estimated as 4800 and 1.8, respectively. The obtained polymer is found to have the extended π-conjugated backbone and relatively low-lying lowest unoccupied molecular orbital (LUMO) energy level (-3.12 eV), which is supported by its UV-vis absorption spectrum and cyclic voltammetric (CV) analysis. In addition, the stannole-containing polymer is found to be applicable to a chemosensor for fluoride anion where the color and photoluminescence intensity of the polymer solution exhibits a distinct change in the presence of a fluoride anion.
通过对区域规整的有机钛聚合物进行后元素转化，合成了含锡二噻吩-2,5-二基的π共轭聚合物。例如，通过区域规整的有机钛聚合物与二苯基二氯化锡的反应，可以得到收率为 83%的含 1,1-二苯基锡二噻吩的聚合物。该区域规整的有机钛聚合物是由 1,4-双(2-乙基己氧基)-2,5-二乙炔基苯和低化合价钛配合物在-50°C 至环境温度下制备得到的。含锡聚合物的数均分子量和分子量分布（M 和 M/M）分别估计为 4800 和 1.8。通过紫外可见吸收光谱和循环伏安法（CV）分析，发现所得到的聚合物具有扩展的π共轭主链和较低的最低未占据分子轨道（LUMO）能级（-3.12 eV）。此外，还发现含锡聚合物可用作氟阴离子的化学传感器，聚合物溶液的颜色和荧光强度在存在氟阴离子时会发生明显变化。
