CN111892605B - 新型五元环苝二酰亚胺分子材料及其制备方法与应用 - Google Patents
新型五元环苝二酰亚胺分子材料及其制备方法与应用 Download PDFInfo
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/06—Peri-condensed systems
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Abstract
本发明公开了两种五元环苝二酰亚胺分子体系及其制备方法与其在场效应晶体管器件中的应用。本发明化合物的结构式如式Ⅰ和式Ⅰ’所示:所述式I中,R1和R2均选自C6‑C18的直链烷基,苯基,2,6‑二异丙基苯基中的任意一种,且R1和R2相同。杂原子X为氧原子、硫原子和氮原子中任意一种。本发明提供的两种五元环苝二酰亚胺异构体的合成方法及其在场效应晶体管中的应用。通过两步简单的反应分离得到两种五元环苝二酰亚胺,均表现出n型半导体性能,PDI39和PDI310的电子迁移率分别达到0.0016和0.036cm2V‑1s‑1,并且开关比均大于106。
Description
技术领域
本发明具体涉及新型五元环苝二酰亚胺分子的开发、新制备方法的发展及其在场效应晶体管中的应用,属于共轭小分子n-型半导体材料领域。
背景技术
有机场效应晶体管作为一种重要的逻辑器件,在柔性显示,射频识别,集成电路,电子皮肤,记忆存储等方面具有重要应用。相对于无机场效应晶体管,有机场效应晶体管因具有柔性,质轻,可大面积制备等优势受到越来越多的研究人员的广泛关注。有机半导体作为有机场效应晶体管器件中的活性层对其性能起着至关重要的作用。在过去的几十年中,p型半导体材料研究相对成熟,很多p型半导体材料的空穴迁移率达到了非晶硅水平。然而n型半导体材料的研究相对滞后,迁移率大于1cm2V-1s-1的n型材料还较为缺乏。为构建更为高效的逻辑器件,需要平衡p型和n型半导体性能。因此合成一些新型具有高迁移率n型半导体材料是非常有必要的。
发明内容
本发明的目的在于提供一种五元环苝二酰亚胺化合物及其制备。
本发明所提供的五元环苝二酰亚胺化合物,其结构式如式Ⅰ或式Ⅰ’所示:
所述式I或式Ⅰ’中,R1和R2相同,可选自C6-C18的直链烷基(具体可为-C6H13)、取代或未取代的苯基中的任意一种,
所述取代的苯基中的取代基可选自C1-C6的支链或支链烷基、C1-C6的烷氧基、氟、氯、溴和碘中的至少一种,具体可为2,6-二异丙基;
杂原子X为氧原子、硫原子和氮原子中任意一种。
上述式Ⅰ或式Ⅰ’所示化合物具体可为:
上述式I和式Ⅰ’所示的五元环苝二酰亚胺化合物通过包括如下步骤的方法制备得到:
1)由式Ⅱ所示化合物在二氯亚砜中反应,得到式Ⅲ所示化合物;
2)在催化剂存在下,使得式Ⅲ所示化合物与式Ⅳ所示化合物发生傅克反应,得到含式Ⅰ和式Ⅰ’所示化合物的混合物,分离纯化即得到式Ⅰ和式Ⅰ’所示化合物,
式Ⅳ中,R与式Ⅰ中R1、R2均相同,X与式Ⅰ中的X相同。
上述方法步骤1)中,式Ⅱ所示化合物表示perylene-3,9-dicarboxylic acid与perylene-3,10-dicarboxylic acid的混合物,市售;
所述反应的温度可为90~110℃,具体可为110℃;时间可为12-48h,具体可为24h;
第一步反应完成后直接除去多余溶剂,参与第二步反应;
上述方法步骤2)中,所述催化剂可为氯化铝,氯化铁,三氟甲磺酸钪中的一种;具体可为氯化铝;
式III所示化合物、式IV所示化合物、所述催化剂的摩尔比依次可为1:8~30:4~10;
所述傅克反应的反应温度可为110~180℃,具体可为160℃,反应时间可为12~48h,具体可为24h;
所述傅克反应在有机溶剂中进行;
所述有机溶剂具体可为氯苯,1,2-二氯苯中的一种;
上述方法步骤2)可在氮气或空气气氛下进行。
所述分离纯化的操作为:将所述傅克反应后的体系直接用柱色谱进行分离,即,先用石油醚做洗脱剂除去体系溶剂,再用石油醚/二氯甲烷(3:1~0:1,体积比)作洗脱剂得到式Ⅰ和式Ⅰ’所示化合物的混合物,将该混合物溶解在氯仿溶剂中,缓慢加入甲醇至刚好有固体析出,静置一段时间后过滤出固体,用甲醇清洗得到所述式Ⅰ所示化合物PDI39;将剩余溶液再通过柱色谱分离,氯仿溶剂中,缓慢加入甲醇至刚好有固体析出,静置一段时间后过滤出固体,反复重结晶3-4次,得到所述式Ⅰ’所示化合物PDI310。
本发明的另一目的是提供上述式Ⅰ或式Ⅰ’所示化合物作为n-型半导体材料的应用。
所述应用具体可为式Ⅰ或式Ⅰ’所示化合物在制备场效应器件中的应用。
所述场效应晶体管器件表现n型电荷传输性能。
本发明还提供了一种场效应器件及其制备方法。
本发明所提供的场效应器件,以上述式Ⅰ或式Ⅰ’所示化合物为n型半导体材料。
所述场效应器件通过包括如下步骤的方法制备得到:
将上述式Ⅰ或式Ⅰ’所示化合物蒸镀到衬底上制成所述场效应器件;
所述场效应器件的制备和测试为氮气氛围;
所述衬底为为本领域公知的常用衬底,电极为金电极,经十八烷基三氯硅烷(OTS)修饰并清洗完成后,放置于对甲基苯硫酚乙腈溶液中浸泡10h。
本发明具有以下优点:
本发明提供的式I和式Ⅰ’所示化合物,具有优良的电子传输性能以及溶解性能,有利于研究其半导体性能。同时,两种异构体由于五元环二酰亚胺位置不同造成的光电性能差异对于研究二酰亚胺类化合物的构效关系提供了材料。两种异构体易于衍生化,有利于构建共轭程度更大,性能更好的半导体材料。
附图说明
图1为本发明中式Ⅰ和式Ⅰ’所示化合物的制备方法。
图2为本发明实施例1中式I和式Ⅰ’所述化合物的晶体结构。图2(a)为PDI39的晶体结构和堆积,图2(b)为PDI310的晶体结构和堆积。
图3为本发明实施例1中制备的式I和式Ⅰ’所示化合物氯仿溶液的紫外-可见吸收光谱和荧光发射光谱。
图4为本发明实施例2中制备的式I和式Ⅰ’所示化合物的循环伏安曲线。
图5为本发明实施例2中制备的式I和式Ⅰ’所述化合物的转移曲线和输出曲线;其中图5(a,c)为转移曲线,图5(b,d)为输出曲线,图5(a,b)为化合物PDI39的测试结果,图5(c,d)为化合物PDI310的测试结果。
具体实施方式
下面通过具体实施例对本发明进行说明,但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、材料等,如无特殊说明,均可从商业途径得到。
下述实施例中化合物1表示perylene-3,9-dicarboxylic acid与perylene-3,10-dicarboxylic acid的混合物,购自郑州阿尔法化工有限公司。
实施例1、式Ⅰ和式Ⅰ’所示化合物的合成(式Ⅰ中,R1和R2均为正己基):
化学反应流程图如图1所示,具体反应步骤条件如下:
向化合物1(2.94mmol)中加入30ml氯化亚砜,加热至110°反应24h,停止反应。用旋转蒸发仪除去剩余氯化亚砜,得到化合物2。再向2中加入氯化铝(9.64mmol)和1,2-二氯苯30ml,室温搅拌3min后加入己基异氰酸酯(44.1mmol),加热至160℃反应24h,反应停止后,用柱色谱和重结晶的方法分离得到产物PDI39(0.439mmol,产率:15%)和PDI310(0.382mmol,产率:13%);
结构确证数据如下:
化合物PDI39:
1H NMR(500MHz,CDCl2CDCl2)δ(ppm):8.96(d,J=8.5Hz,2H),8.57(s,2H),8.51(d,J=7.5Hz,2H),7.83(t,J=8.0Hz,2H),3.79(t,J=7.5Hz,4H),1.78-1.84(m,4H),1.37–1.48(m,12H),0.96(t,J=7.0Hz,6H);13C NMR(125MHz,CDCl2CDCl2):δ168.94,168.28,137.02,132.56,130.96,130.83,129.90,129.49,126.69,126.07,124.76,113.75,38.34,31.35,28.61,26.57,22.46,13.94;
HR-MS:计算值为C36H34N2O4(M+):558.2519,质谱峰位置:558.2522;
元素分析:计算值为C36H34N2O4:C,77.40;H,6.13;N,5.01。测量值:C,77.26;H,6.13;N,5.08。由上可知,该产物结构正确。
化合物PDI310:
1H NMR(500MHz,CDCl3)δ(ppm):8.69(d,J=8.5Hz,2H),8.29(d,J=7.5Hz,2H),8.23(s,2H),7.68(t,J=8.0Hz,2H),3.63(t,J=7.5,4H),1.73-1.79(m,4H),1.33–1.43(m,12H),0.92(t,J=7.0Hz,6H);13C NMR(125MHz,CDCl3):δ168.18,167.65,134.91,131.27,130.27,129.81,129.75,128.46,125.90,124.67,123.07,113.60,38.32,31.60,28.85,26.84,22.78,14.23;
HR-MS:计算值为C36H34N2O4(M+):558.2519,质谱峰位置:558.2521;
元素分析:计算值为C36H34N2O4:C,77.40;H,6.13;N,5.01。测量值:C,77.20;H,6.20;N,5.00。由上可知,该产物结构正确。
实施例2、式Ⅰ和式Ⅰ’所示化合物的晶体结构和堆积:
晶体的制备:将化合物溶于氯仿溶液,通过扩散法向氯仿溶液中缓慢扩散甲醇得到。
本发明化合物的晶体结构和堆积如图2所示,两个异构体均具有较好的平面性。PDI310(b)表现出典型的鱼骨状堆积,分子间表现出较强的π-π相互作用,π-π距离为PDI39(a)表现出二维堆积结构,分子间存在的主要为氢键相互作用和较弱的π-π相互作用,其π-π距离和PDI310相近,C-H…O的距离为
实施例3、式I和式Ⅰ’所述化合物在氯仿溶液中的紫外-可见吸收光谱和荧光发射光谱:
将本发明实施例1中制得的化合物(式I和式Ⅰ’所示化合物)溶于多种有机溶剂,有机溶剂包括氯仿、邻二氯苯、1,1,2,2-四氯乙烷,以及其他溶剂,如:甲苯。本发明化合物在氯化溶剂中具有良好地溶解度。通过将式I和式Ⅰ’所示化合物溶于氯仿溶液测得溶液吸收和发射光谱如图3所示。由图3可知,PDI39的最大吸收和发射波长分别是510nm和530nm。PDI310的吸收波长和发射相较于PDI39发生了明显的红移,分别为530nm和556nm。
实施例4、利用循环伏安法测前线轨道能级(LUMO):
利用电化学工作站对本发明实施例1制得的式Ⅰ和式Ⅰ’所示化合物的电化学特性进行了测试,用三电极测试体系,玻璃碳电极为工作电极,Ag/AgCl电极为参比电极,铂丝电极为对电极。以四丁基六氟磷酸铵为支持电解质,以二茂铁为内标,扫描速率为100mv/S的条件测试了PDI39和PDI310的超干二氯甲烷溶液的循环伏安特性曲线,如图4所示。由图4可知,两个化合物均表现出两个可逆的还原峰,PDI39和PDI310的LUMO能级分别为-3.59V和-3.70V。
实施例5、场效应器件的制备:
根据文献(Chem.Rev.2012,112,2208-2267)的方法,在单晶硅上镀一层300nm厚的二氧化硅,再用光蚀刻的方法镀金,宽度1440微米,长度为5、10、20、30、40、50微米,先用十八烷基三氯硅烷单分子层进行修饰,然后用对甲基苯硫酚进行修饰,然后将在本发明实施例1中制得的化合物蒸镀到以上修饰好的薄片上。将蒸镀时的衬底温度控制在50℃、80℃、100℃,制备得到化合物的场效应器件,并测试其场效应性质;
其中衬底温度为80℃时制备的场效应器件的输出曲线(b,d)和转移曲线(a,c)如图5所示。在氮气氛围下,两化合物均表现出n型半导体性质,具有较大的开关比,并且PDI310(c,d)的迁移率高于PDI39(a,b)。由结果可以看出,本发明通过两步简单的反应,实现了两种五元环苝二酰亚胺异构体的合成。通过对比两种异构体光电性能差异,本发明实现了改变苝环功能化位点来调节其半导体性能。
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