CN109336776B - 一种以三芳胺为端基的大位阻烷氧基取代共轭化合物及其应用 - Google Patents
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物及其应用 Download PDFInfo
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Abstract
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，涉及有机合成领域，其结构式I如下所示：
其中，Ar为苯基、萘基或蒽基，R1为H、CH3或OCH3，R2为大位阻烷氧链。本发明选择以稳定性较好的有机三芳胺为氧化还原活性端基，以缠有树枝状烷氧基团的共轭配体为桥链，合成了大位阻烷氧链附着的化合物。通过电化学试验可知，本发明中的三芳胺共轭化合物的端基之间具有极强的电子相互作用，电荷传输能力较佳，尤为适合应用于绝缘分子导线中。
Description
技术领域
本发明涉及有机合成领域，特别涉及到一种以三芳胺为端基的大位阻烷氧基取代共轭化合物及其应用。
背景技术
分子导线是分子电子器件连接桥梁和实现电子器件微型化的关键单元，大量研究结果表明分子导线的电荷传输能力随着分子长度的增加，呈指数衰减。三芳胺具有优良的电化学活性以及稳定性，近年来科学家们以其作为端基合成了不少新的化合物，并期待这些化合物具有良好的电荷运输能力。但是事与愿违的是，实践证明大部分的以三芳胺为端基的化合物的电子相互能力较弱，其制成的绝缘分子导线的性能也难以达到相关的应用标准。
发明内容
本发明的目的在于提供一种端基之间具有极强电子相互作用的以三芳胺为端基的大位阻烷氧基取代共轭化合物。
为了解决上述技术问题，本发明采用如下技术方案：一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，结构式I如下所示：
其中，Ar为苯基、萘基或蒽基，R1为H、CH3或OCH3，
R2为
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，结构式I-1如下所示：
相应的制备方法包括以下步骤：向容器中加入4-硼酸酯-4',4'-二甲氧基三苯胺、2,5-二(4-叔丁基苄氧基)-1,4-二碘苯、四(三苯基膦)钯，然后在氮气保护下加入已脱气的甲苯、乙醇及2mol/L的碳酸钾溶液，再于110℃下回流24h后，待体系冷却至室温，经硅藻土过滤得滤液，旋干，进行柱层析分离后即得。
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，结构式I-2如下所示：
相应的制备方法包括以下步骤：往容器中加入4-硼酸酯-4',4'-二甲氧基三苯胺、树枝状基团保护的1,4-二碘苯、四(三苯基膦)钯，抽充N2三次，然后在氮气保护下加入已脱气的甲苯、乙醇及2mol/L的碳酸钾溶液，再于110℃下回流24h后，待体系冷却至室温，经硅藻土过滤得滤液，旋干，进行柱层析分离后即得。
在以上两种大位阻烷氧基取代共轭化合物的制备过程中，柱层析分离时所用洗脱剂由体积比为1:1的二氯甲烷和石油醚组成，所用硅胶的目数为200-300目。
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，结构式Ⅱ如下所示：
其中，Ar为苯基、萘基或蒽基，R1为H、CH3或OCH3，
R2为
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，结构式Ⅱ-1如下所示：
相应的制备方法包括以下步骤：向容器中加入4-乙炔基三苯胺和2,5-二(4-叔丁基苄氧基)-1,4-二碘苯、四(三苯基膦)钯、碘化亚铜，然后在氮气保护下加入已脱气的四氢呋喃及三乙胺，再于80℃下回流24h，待体系冷却至室温后，经硅藻土过滤得滤液，旋干，进行柱层析分离后即得。
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，结构式Ⅱ-2如下所示：
相应的制备方法包括以下步骤：向容器中加入4-乙炔基三苯胺、树枝状基团取代的1,4-二碘苯、四(三苯基膦)钯、碘化亚铜，然后在氮气保护下加入已脱气的四氢呋喃及三乙胺，再于80℃下回流24h，待体系冷却至室温后，经硅藻土过滤得滤液，旋干，进行柱层析分离后即得。
在以上两种大位阻烷氧基取代共轭化合物的制备过程中，柱层析分离时所用洗脱剂由体积比为1:2的二氯甲烷和石油醚组成，所用硅胶的目数为200-300目。
本发明提供的三芳胺共轭化合物可应用于制作分子导线材料。
和现有技术相比，本发明具有以下有益效果：本发明选择以稳定性较好的有机三芳胺为氧化还原活性端基，缠有树枝状烷氧基团的共轭配体为桥链，合成了大位阻烷氧链附着的化合物。通过电化学试验可知，本发明中的三芳胺共轭化合物的端基之间具有极强的电子相互作用，电荷传输能力较佳，尤为适合应用于绝缘分子导线中。
具体实施方式
下面给出实施例以对本发明进行具体的描述，有必要在此指出的是以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的普通技术人员根据该实施例对本发明所做出的一些非本质的改进或调整仍属于本发明的保护范围。
实施例1
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，该化合物通过缠有树枝状烷氧基团的苯基桥联，其制备方法如下：
往50mL双颈烧瓶中加入0.46mmol 4-硼酸酯-4',4'-二甲氧基三苯胺(200mg)、0.21mmol 2,5-二(4-叔丁基苄氧基)-1,4-二碘苯(137mg)、0.01mmol四(三苯基膦)钯(12mg)，体系抽充N2三次，然后在氮气保护下加入已脱气的10mL甲苯、2mL乙醇及2mL 2mol/L的碳酸钾溶液，再于110℃下回流24h后，体系冷却至室温，经硅藻土过滤得滤液，旋干，柱层析分离，得到112mg结构式为I-1的黄色固体，产率：53％。
柱层析分离过程中，所用硅胶为200-300目，所用洗脱剂选用体积比为1:1的二氯甲烷和石油醚。
结构式I-1如下所示：
元素分析(C68H68N2O6)：理论值：C，80.92；H，6.79。测定值：C，80.81；H，6.85。
结构数据：1H NMR(500MHz,CDCl3):δ1.32(s,18H,CH3),3.80(s,12H,-OCH3),4.97(s,4H),6.85(d,J(HH)＝5.0Hz,6H),6.98(d,J(HH)＝5.0Hz,4H),7.06(s,2H),7.11(d,J(HH)＝10.0Hz,7H),7.27(s,2H),7.34-7.38(m,7H),7.43(d,J(HH)＝10.0Hz,4H),7.69(s,2H).
13C NMR(125MHz,CDCl3):δ31.36,34.53,55.48,71.70,114.64,117.09,120.14,125.24,126.50,127.05,127.64,130.08,130.22,130.69,134.49,135.21,141.06,147.61,150.41,150.51,155.76。
实施例2
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，该化合物通过缠有树枝状烷氧基团的苯基桥联，其制备方法如下：
往50mL双颈烧瓶中加入1.71mmol 4-硼酸酯-4',4'-二甲氧基三苯胺(737mg)、树枝状基团保护的0.81mmol 1,4-二碘苯(965mg)，0.08mmol四(三苯基膦)钯(94mg)，体系抽充N2三次，然后在氮气保护下加入10mL已脱气的甲苯、2mL乙醇及2mol/L的碳酸钾溶液，再于110℃下回流24h后，体系冷却至室温，过滤(经硅藻土)得滤液，旋干，柱层析分离，得到200mg结构式为I-2的白色固体，产率：64％。
柱层析分离过程中，所用硅胶为200-300目，所用洗脱剂选用体积比为1:1的二氯甲烷和石油醚。
结构式I-2如下所示：
元素分析(C104H108N2O10)：理论值：C，80.80；H，7.04。测定值：C，80.91；H，6.97。
结构数据：1H NMR(500MHz,CDCl3):δ1.31(s,36H,-CH3),3.76(s,12H,-OCH3),4.92(s,8H,-CH2),4.99(s,4H,-CH2),6.52(s,2H),6.63(s,4H),6.78(d,J(HH)＝10.0Hz,4H),6.98(d,J(HH)＝5.0Hz,4H),7.04(t,J(HH)＝10.0Hz,10H),7.30(d,J(HH)＝10.0Hz,8H),7.37(d,J(HH)＝10.0Hz,8H),7.47(d,J(HH)＝10.0Hz,4H)。
13C NMR(125MHz,CDCl3):δ31.31(CH3),31.57,34.54,55.40,69.92,101.41,105.49,114.60,116.57,119.76,125.50,126.61,127.61,129.99,130.07,130.36,133.36,139.91,140.80,147.68,150.10,150.97,155.75,160.06。
实施例3
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，该化合物通过缠有树枝状烷氧基团的苯乙炔基桥联，其制备方法如下：
在50mL双颈烧瓶中加入1.71mmol 4-乙炔基三苯胺(460mg)、2,5-二(4-叔丁基苄氧基)-1,4-二碘苯(530mg，0.81mmol)、0.17mmol四(三苯基膦)钯(94mg)，0.17mmol碘化亚铜(15mg)，体系抽充N2三次，然后在氮气保护下加入已脱气的20mL四氢呋喃及10mL三乙胺，再于80℃下回流24h后，体系冷却至室温，经硅藻土过滤得滤液，旋干，柱层析分离，得到505mg结构式为II-1的黄色固体，产率：67％。
柱层析分离过程中，所用硅胶为200-300目，所用洗脱剂选用体积比为1:2的二氯甲烷和石油醚。
结构式II-1如下所示：
元素分析(C68H60N2O2)：理论值：C，87.14；H，6.45。测定值：C，87.06；H，6.59。
结构数据：1H NMR(500MHz,CDCl3):δ1.30(s,18H,-CH3),5.12(s,4H,-OCH2),6.99(d,J(HH)＝5.0Hz,4H),7.06(t,J(HH)＝10.0Hz,6H),7.12(d,J(HH)＝5.0Hz,8H),7.28(t,J(HH)＝10.0Hz,8H),7.34(d,J(HH)＝10.0Hz,4H),7.39(d,J(HH)＝10.0Hz,4H),7.45(d,J(HH)＝10.0Hz,4H).
13C NMR(125MHz,CDCl3):δ31.36(CH3),34.55,71.53,85.34,95.64,123.55,125.00,125.34,127.01,129.38,147.19,147.93,150.76,153.68。
实施例4
一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，该化合物通过缠有树枝状烷氧基团的苯乙炔基桥联，其制备方法如下：
在50mL双颈烧瓶中加入1.71mmol 4-乙炔基三苯胺(460mg)、0.81mmol树枝状基团取代的1,4-二碘苯(965mg)、0.17mmol四(三苯基膦)钯(94mg)，碘化亚铜(15mg,0.17mmol)，体系抽充N2三次，然后在氮气保护下加入已脱气的20mL四氢呋喃及10mL三乙胺，反应混合物在80℃下回流24h后，体系冷却至室温，经硅藻土过滤得滤液，旋干，柱层析分离，得到810mg结构式为II-2的橙色固体，产率：68％。
柱层析分离过程中，所用硅胶为200-300目，所用洗脱剂选用体积比为1:2的二氯甲烷和石油醚。
所用洗脱剂选用体积比为1:1的二氯甲烷和石油醚。
结构式II-2如下所示：
元素分析(C104H100N2O6)：理论值：C，84.75；H，6.84。测定值：C，84.90；H，6.75。
结构数据：1H NMR(500MHz,CDCl3):δ1.30(s,36H,-CH3),4.95(s,8H,-CH2),5.12(s,4H,-CH2),6.56(t,J(HH)＝5.0Hz,2H),6.81(s,4H),6.95(d,J(HH)＝10.0Hz,4H),7.06(dd,J(HH)＝10.0Hz,14H),7.25(t,J(HH)＝10.0Hz,8H),7.29(d,J(HH)＝5.0Hz,8H),7.36(d,J(HH)＝10.0Hz,8H)，7.39(d,J(HH)＝5.0Hz,4H).
13C NMR(125MHz,CDCl3):δ31.34(CH3),34.56,70.02,71.45,85.18,95.75,101.69,105.83,114.75,116.12,117.90,122.20,123.55,125.01,125.48,127.55,129.38,132.62,133.82,139.53,147.16,147.99,150.98,153.51,160.27。
电化学测量试验
采用设备：电化学工作站CHI 660D(CH Instruments Company,USA)。
以玻碳电极作为工作电极，铂电极作对电极，Ag+|Ag电极为参比电极。以0.001molL-1n-Bu4NPF6的CH2Cl2溶液为电解液，被测底物的浓度0.001mol L-1。
循环伏安通常以扫描速率为100mV s-1测得，方波伏安在f＝10Hz条件下测得。
数据处理：通过OriginPro 8.0将数据处理成图片。
通过电化学方法对大位阻树枝状烷氧基取代共轭有机体进行了循环伏安及方波伏安测试，得到了相应的电化学参数，具体结果如表1所示。
表1实施例1-4中大位阻烷氧基取代共轭化合物的电化学测试数据
| 化合物 | E<sub>1/2</sub>(1)(V) | E<sub>1/2</sub>(2)(V) | ΔE(mV)<sup>b</sup> | K<sub>c</sub><sup>c</sup> |
| I-1 | 0.74 | 0.95 | 210 | 3.50×10<sup>3</sup> |
| I-2 | 0.73 | 0.97 | 240 | 1.12×10<sup>4</sup> |
| II-1 | 0.96 | 1.03 | 70 | 15 |
| II-2 | 0.94 | 1.04 | 100 | 48 |
由表1可知，本发明制备的两类系列化合物(I-1、I-2为第一类，II-1、II-2为第二类)均呈现了两次连续的单电子氧化还原过程，测试得到的两次氧化还原的电位差值ΔE值可达到70-240mV。第一类化合物的电位差值达到了200mV以上，而第二类含炔基类三芳胺化合物由于端基之间距离相对而言较远，测试得到的ΔE值与第一类化合物相比相对较小。本领域的技术人员应该清楚，以上两类系列化合物相对于现有技术均显著提高了端基之间的电子相互耦合作用，在绝缘分子导线领域存在巨大的应用前景。
Claims (5)
1.一种以三芳胺为端基的大位阻烷氧基取代共轭化合物，其特征在于，结构式I如下所示：
其中，Ar为苯基，R1为OCH3，
R2为
2.权利要求1所述以三芳胺为端基的大位阻烷氧基取代共轭化合物的制备方法，其特征在于，制备过程包括以下步骤：
向容器中加入4-硼酸酯-4',4'-二甲氧基三苯胺、2,5-二(4-叔丁基苄氧基)-1,4-二碘苯、四(三苯基膦)钯，然后在氮气保护下加入已脱气的甲苯、乙醇及2mol/L的碳酸钾溶液，再于110℃下回流24h后，待体系冷却至室温，经硅藻土过滤得滤液，旋干，进行柱层析分离后即得结构式为I-1所示的大位阻烷氧基取代共轭化合物：
3.权利要求1所述以三芳胺为端基的大位阻烷氧基取代共轭化合物的制备方法，其特征在于，制备过程包括以下步骤：
往容器中加入4-硼酸酯-4',4'-二甲氧基三苯胺、树枝状基团保护的1,4-二碘苯、四(三苯基膦)钯，抽充N2三次，然后在氮气保护下加入已脱气的甲苯、乙醇及2mol/L的碳酸钾溶液，再于110℃下回流24h后，待体系冷却至室温，经硅藻土过滤得滤液，旋干，进行柱层析分离后即得结构式为I-2所示的大位阻烷氧基取代共轭化合物：
4.根据权利要求2或3所述以三芳胺为端基的大位阻烷氧基取代共轭化合物的制备方法，其特征在于：柱层析分离时，所用洗脱剂由体积比为1:1的二氯甲烷和石油醚组成，所用硅胶的目数为200-300目。
5.权利要求1所述大位阻烷氧基取代共轭化合物在绝缘分子导线材料中的应用。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6107038A (en) * | 1998-08-14 | 2000-08-22 | Agilent Technologies Inc. | Method of binding a plurality of chemicals on a substrate by electrophoretic self-assembly |
| US20140138628A1 (en) * | 2012-11-21 | 2014-05-22 | Xerox Corporation | Electroactive Fluoroacylated Arylamines |
| CN105359289A (zh) * | 2013-07-31 | 2016-02-24 | 富士胶片株式会社 | 光电转换元件及太阳能电池 |
| WO2016072691A1 (ko) * | 2014-11-05 | 2016-05-12 | 덕산네오룩스 주식회사 | 유기전기소자용 조성물을 이용한 디스플레이 장치 및 유기전기소자 |
| CN107056845A (zh) * | 2017-04-25 | 2017-08-18 | 衡阳师范学院 | 苯基桥联的三芳胺及二茂铁端基化合物及其制备方法和应用 |
| CN107275519A (zh) * | 2016-04-06 | 2017-10-20 | 三星显示有限公司 | 有机发光装置 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307282C (zh) * | 2003-05-15 | 2007-03-28 | 中国科学院长春应用化学研究所 | 能量转移型聚（对苯撑乙烯）类高分子发光材料及其制备方法 |
| US20080138635A1 (en) * | 2005-03-02 | 2008-06-12 | Zhikuan Chen | Conjugated Organic Molecules for Molecular Electronic Devices |
-
2018
- 2018-11-27 CN CN201811429343.4A patent/CN109336776B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6107038A (en) * | 1998-08-14 | 2000-08-22 | Agilent Technologies Inc. | Method of binding a plurality of chemicals on a substrate by electrophoretic self-assembly |
| US20140138628A1 (en) * | 2012-11-21 | 2014-05-22 | Xerox Corporation | Electroactive Fluoroacylated Arylamines |
| CN105359289A (zh) * | 2013-07-31 | 2016-02-24 | 富士胶片株式会社 | 光电转换元件及太阳能电池 |
| WO2016072691A1 (ko) * | 2014-11-05 | 2016-05-12 | 덕산네오룩스 주식회사 | 유기전기소자용 조성물을 이용한 디스플레이 장치 및 유기전기소자 |
| CN107275519A (zh) * | 2016-04-06 | 2017-10-20 | 三星显示有限公司 | 有机发光装置 |
| CN107056845A (zh) * | 2017-04-25 | 2017-08-18 | 衡阳师范学院 | 苯基桥联的三芳胺及二茂铁端基化合物及其制备方法和应用 |
Non-Patent Citations (2)
| Title |
|---|
| "核—壳"结构分子线的合成及性质研究;师自法;《中国博士学位论文全文数据库(电子期刊)工程科技I辑》;20071015;第18页倒数第2段；第19页Figure2-4 * |
| Oligo(p-phenyleneethynylene) (OPE) Molecular Wires: Synthesis and Length Dependence of Photoinduced Charge Transfer in OPEs with Triarylamine and Diaryloxadiazole End Groups;Katharine E. Linton，等;《Chem. Eur. J》;20150128;第21卷(第10期);第3998页Scheme 1化合物6；第3999页Scheme 2；Supporting Information第S3页Scheme S2 * |
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