Preparation And Sensing Properties Of Perylenediimide

Due to their excellent chemical,thermal and light stability,perylenediimide derivatives（PTCDIs）are not only still playing a role in traditional dye,but also used in field-effect materials,liquid-crystalline materials,laser dyes,pigment chemical luminescence and solar cells.As one of n-type organic semiconductor materials（electron acceptor）,PTCDIs are capable of acting as sensory materials used to examine some reducing gas（electron donor）.In this dissertation,we have designed and synthesized a series of compounds by modifying PTCDIs,and then we further investigated their behaviors of self assembly in solution and other related properties.The research includes:1.Tuning the sensing performance of PTCDIs through adjusting the crystalline structure,π-π overlap and energy level by the introduction of phenoxy containing different alkyl chain was we hoped.So,N,N′-dicyclohexyl-1,6,7,12-tetra-phenoxy-3,4,9,10-perylenedicarboximide（PH）,N,N′-dicyclohexyl-1,6,7,12-tetra（paratert-butyl-phenoxy）-3,4,9,10-perylenedicarboximide（TPH）and N,N′-dicyclohexyl-1,6,7,12-tetra（para-（1”,1”,3”,3”-tetramethylbutyl）phenoxy）-3,4,9,10-perylenedicarboximide（OPH）were prepared and studied.They have good sensing performance in hydrazine vapor（5 ppm）.The better crystalline structure,smallest torsionangle and activation energy makes OPH sensor the best sensing performance towards hydrazine vapor among these three compounds.TPH sensor exhibiting better sensing performance towards hydrazine vapor due to the best crystalline structure,and smaller interplanar spacing.PH shows the worst sensing performance towards hydrazine vapor because of the largest activation energy and worst crystalline structure.2.Tuning the sensing performance of PTCDIs through adjusting the hydrogen bond and π-π overlap by the introduction of sugar containing inherent chiral centers was we hoped.So,N,N′-bis（（4-aminophenyl）-α-D-glucopyranoside）-1,6,7,12-tetra-（4’-（1",1",3",3"-tetramethylbutyl）phenoxy）-3,4,9,10-perylenedicarboximide（a）,N,N′-bis（（4-aminophenyl）-β-D-glucopyranoside）-1,6,7,12-tetra-（4’-（1",1",3",3"-tetramethylbutyl）phenoxy）-3,4,9,10-perylenedicarboximide（b）and N,N′-bis（4-methylphenyl）-1,6,7,12-tetra（4’-（1",1",3",3"-tetramethylbutyl）phenoxy）-3,4,9,10-perylenedicarboximide（c）as a contrast were synthesized and studied.A right-handed helical supramolecular nanostructures was obtained for a and left-handed helical supramolecular nanostructures of b in THF/H₂O solution.Compared with the achiral group substituted PTCDIs,the chiral group substituted PTCDIs exhibited more enhanced current changes in hydrazine vapor（5 ppm）.Meanwhile,a largerπ-πoverlap and a smallerπ-πinterplanar spacing madeα-D-glucopyranoside-substituted PTCDIs more remarkable increase of electrical current than that ofβ-D-glucopyranoside-substituted one.3.Tuning the sensing performance of PTCDIs through adjusting the hydrogen bond and π-π overlap by the introduction of chiral camphorsulfonic acid by ionic self-assembly was we hoped.So,N,N′-bis（2-（trimethylammonium（1R）-（-）-Camphorsulfonicacid）ethylene）perylene-3,4,9,10-tetracarboxyldiimi-de（PR）and N,N′-bis（2-（trimethylammonium（1S）-（+）-10-Camphorsulfonicacid）ethylene）perylene-3,4,9,10-tetracarboxyldiimide（PS）were synthesized and studied.The UV-Vis and CD results show that the aggregates of the complex were formed mainly due to theπ-πstacking between perylene molecules in mixed solvent.In addition,we found that the current of PS reached 0.18μA under the atmosphere of 100ppm ethylenediamine gas,but PR only reached 1.6×10^-2μA;the responsetime and recovery time of PR sensor device are very low as 9 s and 7 s,but the limit of detection is 1.07 ppm.Compared with PR,the response time and recovery time of PS sensor device were found to be 11 s and 14 s,the limit of detection unexpectedly was found to be 0.86 ppm.The results show that a largerπ-πoverlap made PS more remarkable increase of electrical current than PR.