吸电子基对苝酰亚胺衍生物气敏传感性能的影响

Effect of Core-substituted Withdrawing Groups on the Sensory Property of Perylenediimide Derivatives

在苝四酸酐苝湾1,7或1,6,7,12位分别引入氰基或氯原子,制备了两种苝湾含吸电子基的苝酰亚胺衍生物N,N’-双(十二烷基)-1,7-二氰基-3,4:9,10-苝二酰亚胺(PTCDI-CNC12)和N,N’-双(十二烷基)-1,6,7,12-四氯-3,4:9,10-苝二酰亚胺(PTCDI-ClC12),并研究了两种化合物在氯仿/甲醇二元混合溶剂中的超分子自组装及所得纳米结构的传感性能.结果显示,在苯肼气氛(10ppm)中,两种苝酰亚胺衍生物的灵敏度不同,PTCDI-CNC12电流增加了2个数量级,而PTCDI-ClC12增加了4个数量级.其原因在于两者比表面积的差别和分子骨架结构扭曲程度的不同.这表明苝湾位吸电子基对苝酰亚胺衍生物气敏传感性能有着显著影响.

Two perylenediimide derivatives, N, N＇-bis （n-dodeeyl）-1, 7-dicyanoperylene-3, 4：9, 10-tetracarboxyldiimide （PTCDI-CNC12） and N, N ＇-bis （n-dodecyl） 1, 6, 7, 12-tetrachloroperylene-3, 4： 9, 10-tetracarboxyldiimide （PTCDI-C1C12） bearing cyano or chlorine atoms on the 1, 7 or 1, 6, 7, 12-bit at Perylene Bay （bay-area） were prepared, their super molecular self-assembly was studied in chloroform/methanol solution. The determination of sensing properties based on their conductometric gas sensors composed of single nanobelt revealed that the current increased was four orders of magnitude for core-tetrachlorinated peryienediimide derivative and two orders of magnitude for core-dicyanated one in phenylhydrazine vapor （10 ppm）. The differential response to phenylhydrazine vapor was less dependent on specific surface area, and should be ascribed to the difference in twisted skeleton that originates from different bay-substituted groups. Discussion for structure-function relationship suggests core-substitutes withdrawing groups have significant impact on the performance of perylenediimide derivatives gas sensing device by modulating structure of skeleton.