基于柱[5]芳烃的新型双-[1]轮烷的设计与合成

引用本文: 张润淼, 王陈威, 孙晶, 颜朝国, 姚勇. 基于柱[5]芳烃的新型双-[1]轮烷的设计与合成[J]. 有机化学, 2019, 39(12): 3483-3489. doi: 10.6023/cjoc201906006 shu

Citation: Zhang Runmiao, Wang Chenwei, Sun Jing, Yan Chaoguo, Yao Yong. Design and Construction of Pillar[5]arene-Based Bis-[1]rotaxane[J]. Chinese Journal of Organic Chemistry, 2019, 39(12): 3483-3489. doi: 10.6023/cjoc201906006 shu

基于柱[5]芳烃的新型双-[1]轮烷的设计与合成

张润淼 ^a,b, ,
王陈威 ^b, ,
孙晶 ^a, ,
颜朝国 ^{a,
,} ,
姚勇 ^{b,
,}

a.
扬州大学化学化工学院江苏扬州 225000
b.
南通大学化学化工学院江苏南通 226019

通讯作者: 颜朝国, cgyan@yzu.edu.cn; 姚勇, yaoyong1986@ntu.edu.cn

基金项目:

国家自然科学基金（Nos.21801139，21871227）、江苏省自然科学基金（No.BK20180942）、南通大学高层次人才启动基金（No.03083004）、南通大学大型仪器平台开放基金（No.KFJN1814）资助项目

摘要: 以不同长度的亚烷基二胺单元作为柱[5]芳烃边缘侧链的一系列柱[5]单酰胺衍生物，在氯仿中能够形成准[1]轮烷.基于这一中间体准[1]轮烷的合成，通过柱[5]单酰胺衍生物和双水杨醛的缩合反应，成功构建了8个柱芳烃的机械自锁分子（MSMs），即双-[1]轮烷.通过多种方法详细地对新合成的双-[1]轮烷进行了研究，包括¹H NMR，¹³C NMR，2D NOESY NMR和MS分析，发现这类新型MSMs与Cu²⁺有较强的识别作用，两者之间以1:2进行络合.

关键词:

English

Design and Construction of Pillar[5]arene-Based Bis-[1]rotaxane

a.
College of Chemistry and Chemistry Engineering, Yangzhou University, Yangzhou, Jiangsu 225000
b.
College of Chemistry and Chemistry Engineering, Nantong University, Nantong, Jiangsu 226019

Corresponding author: Yan, Chaoguo, E-mail: cgyan@yzu.edu.cn; Yao, Yong, E-mail: yaoyong1986@ntu.edu.cn

Received Date: 06 June 2019
Revised Date: 30 July 2019
Available Online: 25 December 2019
Fund Project:

Project supported by the National Natural Science Foundation of China (Nos. 21801139, 21871227), the Natural Science Foundation of Jiangsu Province (No. BK20180942), the Natural Science Foundation of Nantong University for High-Level Talent (No. 03083004), and the Large Instruments Open Foudation of Nantong University (No. KFJN1814)

Abstract: A series of pillar[5]arene monoamide derivatives with different lengths of alkylenediamine unites as the side chains on the pillar[5]arene's rim can form pseudo[1]rotaxanes. Thus, based on the construction of this intermediate of pseudo[1]rotaxane, eight pillar[5]arene-baed mechanically interlocked molecules (MIMs) of bis-[1]rotaxane were successful constructed through condensation reaction of pillar[5]arene monoamide derivative and salicylaldehyde. The newly synthesized bis-[1]rotaxane was investigated in detail by various methods, including ¹H NMR, ¹³C NMR, 2D NOESY NMR and MS analysis. It was found that this kind of MIMs has a strong recognition effect with Cu²⁺, which complexed by 1:2.

Key words:

随着冠醚^[1]作为第一代超分子大环主体化合物的出现, 超分子化学^[2]逐渐成为许多科学家研究的重要领域之一, 在纳米科学、材料科学和生物科学等领域得到广泛应用^[3].机械互锁分子(MIMs)^[4]已经在超分子化学中得到了广泛的研究, 为先进的超分子系统^[5](如轮烷^[6]、索烃^[7]、分子梭^[8]、开关^[9]和探针^[10])的构建提供了无限的可能, 也使超分子化学适用于分子机器^[11]、化学探针^[12]和药物输送^[13]的构建.虽然MIMs的研究近些年快速发展, 但一类新型的机械MIMs, 即自锁分子(MSMs)的研究报道却很少, 这是由于MSMs的轴和外圈的轮在一个分子中, 其合成分离较为复杂, 限制了机械自锁分子的快速发展.在有限的机械自锁分子中, 准[1]轮烷是基本和典型的代表^[14].在构建机械自锁分子的过程中, 主体提供的空腔大小和性质是最关键的.作为冠醚、环糊精、杯芳烃和葫芦脲之后相对较新的大环主体化合物柱[n]芳烃^{[15, 16]}, 由于具有富电子空腔、对称的柱状结构和易于修饰的边缘, 已被广泛应用于构建新的超分子聚合物、分子器件、人工跨膜通道以及化学和物理响应材料^[17].柱[5]芳烃是柱芳烃家族中应用最广泛的一类, 因此, 单官能化柱[5]芳烃是构建准[1]轮烷的最通用的候选化合物^[18].例如, Ogoshi等^[19]报道了基于含有辛基三甲基铵基团的柱[5]芳烃的准轮烷, 其在氯仿中表现出自络合的性质.曹德榕等^[20]报道了基于单酯化柱[5]芳烃的准[1]轮烷, 它可以选择性地结合不同的二卤代烷烃.薛敏等^[21]通过单羧酸官能化的柱[5]芳烃与长链烷基胺的反应, 高产率地制备了基于柱[5]芳烃的[1]轮烷.王乐勇等^[22]报道了通过缩合反应形成一个基于芳烃的互锁准[1]索烃和准[1]轮烷(一个包括二氨基烷烃和一个酸官能化的柱[5]芳烃, 另一个包括二异氰酸酯和胺官能化的柱[5]芳烃), 它显示出溶剂和客体的不同响应.杨英威等^[23]报道了一种带有咪唑鎓盐基团的单官能化柱[5]芳烃, 即使在氯仿中高浓度也能形成稳定的准[1]轮烷.近期, 刘育等^[24]报道了基于几个柱[5]芳烃的准[1]索烃, 其中柱芳烃环由两个酰胺基团连接.

我们课题组^[25]成功合成单官能化柱[5]芳烃席夫碱、尿素、吡啶亚胺衍生物, 在结构确定过程中, 发现这些单官能化柱[5]芳烃在溶液和固体状态下均可以发生自络合形成较稳定准[1]轮烷.基于此, 2016年, 我们^[26]报道了一种基于二烯基柱[5]芳烃的准[1]轮烷, 并研究了自锁准[1]轮烷的稳定性.最近, 我们课题组^[27]成功实现以三联吡啶封端的自锁[1]轮烷, 并探究了形成[1]轮烷的条件.在本项研究中, 先合成了柱[5]单酰胺衍生物准[1]轮烷, 然后末端的胺基与双水杨醛类物质^[28]进行缩合反应得到目标产物双-[1]轮烷.

1. 结果与讨论

1.1 目标化合物的合成

目标化合物基于柱[5]芳烃的双-[1]轮烷的合成路线如Scheme 1所示.首先, 进行化合物1与丙、丁二胺和己二胺以1:1化学计量比反应, 得到较为稳定的准[1]轮烷.在制备准轮烷的过程中, 二胺化合物的投料是1的20倍, 以保证二胺化合物的一个胺基和化合物1反应.通过¹H NMR研究可以观察到在负方向的化学位移信号, 表明胺基烷烃链穿入柱[5]芳烃的空腔内, 然后这些中间体准轮烷与化合物2a~2c经过缩合反应, 以可观产率获得基于桥联柱[5]芳烃的双-[1]轮烷3a~3h.

1.2 目标化合物的表征

双[1]轮烷3a~3h通过¹H NMR、¹³C NMR、2D NMR (¹H-¹H NOESY NMR)、IR和高分辨质谱MS等手段进行表征.在席夫碱桥联双柱[5]芳烃3a~3h的¹H NMR谱图的负场方向, 可以明显观察到一些信号峰. 8种双[1]轮烷在负场方向氢的个数如表 1所示. 图 1表示3a在CDCl₃中的¹H NMR谱, 根据负场中的质子数, 将它们归属于3a的胺基烷烃链上质子H_1-4, 由于相应的CH₂受到柱芳烃空腔的电子云的屏蔽作用从而使化学位移向高场移动(Δδ ＝－0.07~－2.27), 这说明两个胺基烷烃链穿入柱芳烃的两个空腔中, 表明形成了[1]轮烷.这一结论是与我们课题组之前合成的基于单酰胺功能化柱[5]芳烃的[1]轮烷所得结论一致^[29].在2D NOESY NMR图谱(图 2)中, 明显观察到己基质子H_1-4与3a的柱[5]芳烃侧链亚甲基质子H_a(图 2, A、B、C、D)、H_1-4与NH质子H_b(图 2, E、F)以及H_1-4与苯环质子H_c (G、H、I、J)之间存在明确的相关信号, 这也证实了烷基链穿入柱芳烃空腔中, 形成了双-[1]轮烷的机械互锁结构.其他7个基于柱芳烃的双-[1]轮烷同样通过以上手段进行表征.通过对比发现双-[1]轮烷中氢在δ 0以下出峰的位置和个数与烷基二胺的链长n有关, 进一步说明柱芳烃套在烷基二胺的烷基链上.

表 1

表 1 8个双[1]轮烷产率及核磁对比

Table 1. Yields of bis[1]rotaxanes and their difference on ¹H NMR

下载: 导出CSV

Compd.	n	m	Yield/%	Number of H (δ＜0)
3a	4	1	66.5	16 (CH₂)
3b	4	2	54.6	16 (CH₂)
3c	2	1	83.4	8 (CH₂)
3d	2	2	65.3	8 (CH₂)
3e	2	4	64.3	8 (CH₂)
3f	1	1	81.1	8 (CH₂)
3g	1	2	65.2	8 (CH₂)
3h	1	4	52.6	8 (CH₂)

图 1

图 1. 双[1]轮烷3a的核磁氢谱部分图(400 MHz, 298 K, CDCl₃)

Figure 1. Partial ¹H NMR spectrum (400 MHz, 298 K, CDCl₃) of bis-[1]rotaxane 3a

下载: 全尺寸图片幻灯片

图 2

图 2. 双[1]轮烷3a的¹H-¹H NOESY图谱(600 MHz, 298K, CDCl₃)

Figure 2. ¹H-¹H NOESY spectrum (600 MHz, 298 K, CDCl₃) of bis-[1]rotaxane 3a

下载: 全尺寸图片幻灯片

图式 1

图式 1. 双-[1]轮烷3a~3h合成路线

Scheme 1. Synthesis of bis-[1]rotaxane 3a~3h

下载: 全尺寸图片幻灯片

1.3 化合物3a的应用

合成的以席夫碱桥联双柱[5]芳烃为骨架的双-[1]轮烷具有亚胺和羟基的结构单元, 可作为识别位点, 通过氢键相互作用可以作为良好的离子结合位点.首先研究了这类化合物对金属离子的选择性(Cu²⁺、Co²⁺、Zn²⁺、Ni³⁺、Cd²⁺和Pb²⁺, c＝1×10^－4 mol/L), 化合物3a在CH₂Cl₂/MeOH中的紫外-可见光光谱数据测定(图 3)表明, 3a具有两个吸收带, 即280 nm附近的强吸收和398 nm处相对较弱的吸收.前者是配体芳环上共轭体系的π-π*跃迁产生, 后者是由碳氮双键的π-π*跃迁产生.在加入金属离子后谱图发生了偏移, 席夫碱桥联的双-[1]轮烷3a对Ni³⁺、Cd²⁺和Pb²⁺几乎没有识别作用, 而对Cu²⁺作用最强.由于Cu²⁺与席夫碱作用, 席夫碱的紫外吸收由原来的390 nm移动至350 nm.通过3a与不同浓度Cu²⁺的紫外滴定实验, 发现两者之间存在着滴定平衡.当Cu(OAc)₂浓度为配体浓度的2倍以后, 谱图不再发生变化, 这说明该席夫碱与铜离子之间存在滴定平衡, 络合比为1:2(图 4).

图 3

图 3. 双[1]轮烷3a与不同金属离子的紫外吸收图

Figure 3. Ultraviolet absorption diagram of bis-[1]rotaxane 3a and different metal ions

下载: 全尺寸图片幻灯片

图 4

图 4. 双[1]轮烷3a与不同浓度的Cu²⁺离子的络合比曲线

Figure 4. Complex ratio curve of bis-[1]rotaxane 3a with differ- rent concentrations of Cu²⁺

下载: 全尺寸图片幻灯片

2. 结论

基于准轮烷的合成, 通过简单的缩合反应, 成功合成了8个以席夫碱桥联的[5]芳烃为骨架的双-[1]轮烷.对于较长的桥联链的双柱[5]芳烃3a~3h, 在溶液中观察到两个柱[5]芳烃单元和桥联链存在穿线行为.此研究扩展了基于柱[5]芳烃的分子系统, 并为合成自锁柱[5]芳烃分子拓展了道路.合成的席夫碱桥联双柱[5]芳烃与不同金属离子存在识别作用, 尤其是对Cu²⁺识别作用最强, 并以1:2比进行络合, 为检测金属离子传感器提供材料支持.

3. 实验部分

3.1 仪器与试剂

除非另有说明, 所有反应均在开放的气氛中进行, 所有试剂均来自商业来源.用Focus X-4装置测定熔点, 未经校正.所有产率均以分离提纯后的计算结果. NMR谱在Ailent 400和AVANCE 600核磁共振波谱仪上测定, 内标为四甲基硅烷(TMS), 以溶剂信号作为内参.在Bruker DPX 600MHz光谱仪上进行2D NOESY实验, 在Bruker maXis超高分辨飞行时间质谱仪测定HR-ESI- MS.

3.2 实验方法

3.2.1 化合物2a~2c的合成

根据报道的方法^[28]合成双水杨醛化合物2a~2c.

3.2.2 化合物3a~3h的合成

根据报道的方法^[25a]合成酰氨基官能化的柱[5]芳烃1a、1b、1c (0.2 mmol), 然后在无水乙醇中加入双水杨醛类化合物2a~2c (0.1 mmol), 2~3 d醋酸, 将混合物加热回流下搅拌6 h.抽滤, 取滤饼, 用乙醇重结晶, 得到纯产物.

双[1]轮烷柱芳烃3a:黄色固体, 产率66.5%. m.p. 165.5~167.4 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.06 (s, 2H, CH＝N), 7.12 (d, J＝8.3 Hz, 2H, ArH), 7.00~6.78 (m, 20 H, ArH), 6.40 (d, J＝9.1 Hz, 4H, ArH), 5.48 (d, J＝7.1 Hz, 2H, NH), 4.60 (s, 4H, CH₂), 4.09 (s, 4H, CH₂), 3.95~3.49 (m, 74H, 48OCH₃, 26CH₂), 2.90 (s, 2H, CH₂), 2.59 (t, J＝8.5 Hz, 4H, CH₂), 2.03 (s, 4H, CH₂), 1.71 (dt, J＝14.6, 7.4 Hz, 4H, CH₂), 1.50 (q, J＝7.4 Hz, 4H, CH₂), 0.92 (t, J＝7.4 Hz, 6H, CH₃), －0.04 (s, 4H, CH₂), －0.62 (s, 2H, CH₂), －0.74 (s, 2H, CH₂), －1.86 (s, 4H, CH₂), －2.24 (s, 4H, CH₂); ¹³C NMR (101 MHz, CDCl₃) δ: 168.63, 167.59, 163.59, 162.30, 150.89, 150.59, 150.46, 150.34, 150.31, 150.27, 150.22, 150.08, 149.95, 146.88, 132.37, 129.30, 129.23, 128.56, 128.41, 128.30, 128.23, 127.81, 127.15, 115.26, 114.44, 114.03, 113.66, 112.92, 112.72, 112.63, 112.14, 112.04, 111.74, 106.66, 102.04, 68.39, 67.48, 65.77, 56.69, 56.18, 56.05, 55.75, 55.71, 55.63, 55.39, 55.20, 55.12, 37.51, 32.01, 30.68, 29.91, 29.11, 29.03, 28.70, 28.51, 27.23, 25.89, 24.29, 22.78, 19.56, 14.05; IR (KBr) v: 3415, 2936, 1688, 1626, 1500, 1466, 1400, 1296, 1213, 1048, 928, 879, 775, 705, 648 cm^－1; HRMS (ESI) calcd for C₁₂₈H₁₅₅N₄O₂₆ ([M+H]⁺): 2165.0950, found 2165.0958.

双[1]轮烷柱芳烃3b:黄色固体, 产率54.6%. m.p. 140.8~142.3 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.05 (s, 2H, CH＝N), 7.11 (d, J＝8.3 Hz, 2H, ArH), 6.98 (s, 4H, ArH), 6.92 (d, J＝5.6 Hz, 6H, ArH), 6.88 (s, 4H, ArH), 6.81 (d, J＝3.7 Hz, 6H, ArH), 6.39 (d, J＝8.4 Hz, 4H, ArH), 5.47 (d, J＝7.9 Hz, 2H, NH), 4.59 (s, 4H, CH₂), 4.03 (t, J＝6.5 Hz, 4H, CH₂), 3.90~3.67 (m, 74H, 48 OCH₃, 26 CH₂), 2.89 (s, 2H, CH₂), 2.59 (t, J＝8.4 Hz, 4H, CH₂), 1.87 (t, J＝8.5 Hz, 8H, CH₂), 1.74~1.67 (m, 4H, CH₂), 1.49 (q, J＝7.4 Hz, 4H, CH₂), 0.92 (t, J＝7.4 Hz, 6H, CH₃), －0.04 (s, 4H, CH₂), －0.63 (s, 2H, CH₂), －0.75 (s, 2H, CH₂), －1.88 (d, J＝25.1 Hz, 4H, CH₂), －2.24 (s, 4H, CH₂); ¹³C NMR (101 MHz, CDCl₃) δ: 168.44, 167.58, 163.68, 162.30, 150.90, 150.59, 150.46, 150.35, 150.32, 150.28, 150.23, 150.08, 149.96, 146.88, 132.31, 129.30, 129.28, 129.23, 128.55, 128.53, 128.41, 128.30, 128.23, 127.81, 127.15, 115.25, 114.43, 114.01, 113.66, 112.92, 112.73, 112.63, 112.15, 112.06, 111.87, 111.69, 106.73, 102.01, 101.92, 68.37, 67.88, 67.83, 65.78, 56.82, 56.17, 56.04, 55.75, 55.70, 55.63, 55.39, 55.19, 55.12, 37.52, 32.01, 30.71, 29.92, 29.07, 29.02, 28.70, 28.52, 27.23, 26.66, 25.90, 25.86, 24.32, 22.80, 19.56, 14.05; IR (KBr) v: 3410, 2937, 2859, 2036, 1681, 1625, 1504, 1459, 1399, 1296, 1212, 1112, 1043, 928, 873, 845, 775, 711, 647, 546 cm^－1; HRMS (ESI) calcd for C₁₃₀H₁₅₉N₄O₂₆ ([M+H]⁺): 2193.1271, found 2193.1276.

双[1]轮烷柱芳烃3c:黄色固体, 产率83.4%. m.p. 194.8~196.1 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 13.20 (s, 2H, OH), 7.23 (s, 2H, ArH), 7.01~6.91 (m, 14H, ArH), 6.83 (d, J＝9.8 Hz, 4H, ArH), 6.77 (s, 4H, 2 ArH, 2 CH＝N), 6.29~6.22 (m, 4H, ArH), 5.45 (s, 2H, NH), 4.59 (s, 4H, CH₂), 4.08 (s, 4H, CH₂), 3.83~3.73 (m, 56H, 48 OCH₃, 8CH₂), 3.71 (s, 6H, CH₂), 3.65 (s, 4H, CH₂), 3.58 (s, 4H, CH₂), 3.40 (s, 4H, CH₂), 2.87 (s, 2H, CH₂), 2.04 (s, 4H, CH₂), 1.80 (s, 4H, CH₂), 1.55 (dd, J＝7.6, 3.6 Hz, 4H, CH₂), 1.00 (t, J＝7.5 Hz, 6H, CH₃), 0.29 (d, J＝43.9 Hz, 4H, CH₂), －0.92 (s, 4H, CH₂), －1.91 (d, J＝31.0 Hz, 4H, CH₂); ¹³C NMR (101 MHz, CDCl₃) δ: 172.60, 167.13, 164.12, 161.56, 151.64, 150.65, 150.61, 150.51, 150.39, 150.31, 150.26, 150.18, 149.59, 147.61, 133.24, 130.76, 129.59, 128.63, 128.54, 128.17, 128.15, 128.09, 127.38, 127.30, 117.94, 114.88, 113.88, 113.78, 113.48, 113.36, 112.97, 112.83, 112.45, 111.93, 111.37, 105.33, 102.25, 70.36, 67.26, 65.70, 55.99, 55.96, 55.91, 55.81, 55.75, 55.61, 55.49, 55.40, 51.15, 36.33, 32.01, 30.48, 29.51, 29.23, 29.04, 28.42, 28.16, 25.97, 25.67, 22.75, 19.48, 14.13; IR (KBr) v: 3415, 2940, 1685, 1624, 1502, 1460, 1399, 1299, 1213, 1112, 1045, 929, 873, 776, 707, 648 cm^－1; HRMS (ESI) calcd for C₁₂₄H₁₄₇N₄O₂₆ ([M+H]⁺): 2109.0346, found 2109.0337.

双[1]轮烷柱芳烃3d:黄色固体, 产率64.3%. m.p. 168.0~170.2 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 7.23 (d, J＝8.5 Hz, 2H, ArH), 7.01 (s, 2H, CH＝N), 7.00~6.88 (m, 12H, ArH), 6.83 (d, J＝9.2 Hz, 4H, ArH), 6.76 (dd, J＝10.0, 2.8 Hz, 4H, ArH), 6.25 (d, J＝10.3 Hz, 4H, ArH), 5.45 (s, 2H, NH), 4.59 (s, 3H, CH₂), 4.14 (s, 2H, CH₂), 4.01 (t, J＝6.5 Hz, 4H, CH₂), 3.96~3.61 (m, 64H, 48OCH₃, 16CH₂), 3.57 (s, 4H, CH₂), 3.39 (s, 4H, CH₂), 2.86 (s, 2H, CH₂), 1.88 (t, J＝6.9 Hz, 4H, CH₂), 1.76 (d, J＝7.3 Hz, 4H, CH₂), 1.60 (s, 4H, CH₂), 1.54 (dd, J＝7.5, 3.7 Hz, 4H, CH₂), 1.00 (t, J＝7.3 Hz, 6H, CH₃), 0.34 (s, 2H, CH₂), 0.23 (s, 2H, CH₂), －0.92 (d, J＝25.7 Hz, 4H, CH₂), －1.90 (d, J＝35.9 Hz, 4H, CH₂); ¹³C NMR (101 MHz, CDCl₃) δ: 172.49, 167.14, 164.23, 161.57, 151.64, 150.65, 150.56, 150.52, 150.39, 150.31, 150.27, 150.19, 149.60, 147.61, 133.20, 130.75, 130.74, 129.59, 128.63, 128.53, 128.47, 128.46, 128.19, 128.16, 128.10, 127.38, 117.90, 114.89, 113.89, 113.70, 113.53, 113.47, 113.39, 113.00, 112.83, 112.50, 112.48, 112.45, 111.94, 111.31, 105.43, 102.22, 70.34, 67.69, 65.70, 55.99, 55.96, 55.92, 55.80, 55.76, 55.57, 55.52, 55.49, 55.39, 51.22, 51.22, 36.34, 36.33, 32.00, 29.46, 29.18, 29.04, 28.40, 26.00, 25.65, 22.76, 19.47, 14.11; IR (KBr) v: 3406, 2940, 2837, 1684, 1625, 1502, 1460, 1399, 1299, 1212, 1044, 928, 877, 776, 707, 649 cm^－1; HRMS (ESI) calcd for C₁₂₆H₁₅₁N₄O₂₆ ([M+H]⁺): 2137.0653, found 2137.0650.

双[1]轮烷柱芳烃3e:黄色固体, 产率65.3%. m.p. 137.8~139.5 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 13.10 (s, 2H, OH), 7.22 (d, J＝8.6 Hz, 2H, ArH), 7.00 (s, 2H, CH＝N), 6.99~6.90 (m, 12H, ArH), 6.82 (d, J＝9.5 Hz, 4H, ArH), 6.77 (d, J＝3.0 Hz, 4H, ArH), 6.27~6.20 (m, 4H, ArH), 5.46 (s, 2H, NH), 4.59 (s, 4H, CH₂), 4.13 (s, 2H, CH₂), 3.98 (t, J＝6.6 Hz, 4H, CH₂), 3.87~3.66 (m, 60 H, 48OCH₃, 12CH₂), 3.57 (s, 6H, CH₂), 3.38 (s, 6H, CH₂), 2.86 (s, 2H, CH₂), 1.81 (dt, J＝16.0, 8.0 Hz, 16H, CH₂), 1.51 (dt, J＝9.2, 4.7 Hz, 8H, CH₂), 0.99 (t, J＝7.4 Hz, 6H, CH₃), 0.33 (s, 2H, CH₂), 0.21 (s, 2H, CH₂), －0.92 (d, J＝28.4 Hz, 4H, CH₂), －1.92 (d, J＝32.5 Hz, 4H, CH₂); ¹³C NMR (101 MHz, CDCl₃) δ: 172.51, 167.14, 164.30, 161.53, 151.63, 150.64, 150.51, 150.39, 150.37, 150.29, 150.25, 150.18, 149.57, 147.58, 133.16, 130.73, 129.57, 128.62, 128.53, 128.51, 128.45, 128.15, 128.08, 127.36, 127.29, 117.89, 114.86, 113.86, 113.48, 113.35, 112.95, 112.82, 112.44, 111.92, 111.24, 105.46, 102.20, 70.32, 67.85, 65.68, 55.98, 55.95, 55.90, 55.80, 55.74, 55.48, 55.39, 51.16, 36.34, 32.00, 30.47, 29.58, 29.46, 29.20, 28.39, 28.13, 26.12, 25.65, 22.75, 19.46, 14.11; IR (KBr) v: 3406, 2936, 2857, 2480, 2035, 1682, 1625, 1503, 1458, 1398, 1298, 1212, 1112, 1043, 929, 875, 776, 711, 648, 550 cm^－1; HRMS (ESI) calcd for C₁₃₀H₁₅₉N₄O₂₆ ([M+ H]⁺): 2193.1293, found 2193.1276.

双[1]轮烷柱芳烃3f:黄色固体, 产率81.1%. m.p. 206.2~208.6 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 13.01 (s, 2H, OH), 7.18 (d, J＝8.7 Hz, 2H, ArH), 7.06~6.79 (m, 18H, ArH), 6.69 (s, 2H, ArH), 6.32 (s, 2H, CH＝N), 6.30~6.22 (m, 4H, ArH), 4.51 (s, 4H, CH₂), 4.32 (d, J＝8.7 Hz, 2H, NH), 4.17~3.22 (m, 80H, 48OCH₃, 32CH₂), 2.03 (s, 4H, CH₂), 1.82 (d, J＝8.4 Hz, 4H, CH₂), 1.58~1.53 (m, 4H, CH₂), 1.00 (t, J＝7.4 Hz, 6H, CH₃), －0.05~－0.20 (m, 4H, CH₂), －1.71 (s, 2H, CH₂), －1.88 (s, 2H, CH₂); ¹³C NMR (101 MHz, CDCl₃) δ: 170.35, 166.77, 163.59, 162.31, 151.46, 150.84, 150.56, 150.49, 150.21, 150.13, 149.71, 148.56, 132.93, 131.73, 129.86, 129.22, 128.55, 128.44, 128.17, 127.87, 127.78, 125.85, 118.09, 114.13, 113.95, 113.93, 113.60, 113.37, 113.21, 112.39, 112.24, 111.57, 105.50, 101.90, 70.37, 67.29, 65.95, 56.10, 55.95, 55.72, 55.61, 55.45, 55.20, 55.18, 55.02, 50.86, 36.06, 31.92, 30.08, 28.62, 28.20, 27.02, 25.97, 19.47, 14.05; IR (KBr) v: 3407, 2934, 1685, 1627, 1499, 1465, 1399, 1296, 1213, 1045, 928, 880, 775, 705, 648 cm^－1; HRMS (ESI) calcd for C₁₂₂H₁₄₃N₄O₂₆ ([M+ H]⁺): 2081.0058, found 2081.0024.

双[1]轮烷柱芳烃3g:黄色固体, 产率65.2%. m.p.154.7~156.2 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 13.00 (s, 2H, OH), 7.16 (d, J＝8.6 Hz, 2H, ArH), 7.04 (d, J＝4.8 Hz, 4H, ArH), 7.01~6.91 (m, 8H, ArH), 6.87 (s, 2H, ArH), 6.81 (d, J＝6.8 Hz, 4H, ArH), 6.68 (s, 2H, ArH), 6.32 (s, 2H, CH＝N), 6.30~6.19 (m, 4H, ArH), 4.50 (s, 4H, CH₂), 4.32 (d, J＝8.5 Hz, 2H, NH), 4.12 (s, 2H, CH₂), 4.07~3.49 (m, 66H, 48OCH₃, 18CH₂), 3.42 (s, 6H, CH₂), 3.26 (s, 6H, CH₂), 1.84 (d, J＝16.8 Hz, 8H, CH₂), 1.55 (q, J＝7.5 Hz, 8H, CH₂), 1.00 (t, J＝7.4 Hz, 6H, CH₃), －0.07~－0.21 (m, 4H, CH₂), －1.72 (s, 2H, CH₂), －1.89 (s, 2H, CH₂); ¹³C NMR (101 MHz, CDCl₃) δ: 221.34, 170.70, 166.82, 163.83, 162.29, 151.47, 150.85, 150.58, 150.51, 150.21, 150.15, 149.71, 148.55, 132.96, 131.71, 129.87, 129.22, 128.59, 128.46, 128.20, 127.86, 127.81, 126.50, 125.85, 118.10, 114.19, 113.94, 113.62, 113.40, 113.23, 112.39, 112.23, 112.18, 111.41, 106.85, 105.61, 101.90, 70.39, 67.73, 65.93, 56.16, 55.96, 55.73, 55.62, 55.48, 55.21, 55.07, 50.68, 36.06, 32.04, 31.92, 30.09, 29.19, 28.60, 28.18, 27.01, 25.99, 19.47, 14.05; IR (KBr) v: 3391, 2935, 1681, 1627, 1499, 1465, 1399, 1297, 1213, 1045, 927, 881, 855, 774, 702, 648 cm^－1; HRMS (ESI) calcd for C₁₂₄H₁₄₇N₄O₂₆ ([M+H]⁺): 2109.0387, found 2109.0337.

双[1]轮烷柱芳烃3h:黄色固体, 产率52.6%. m.p. 142.8~144.9 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 12.99 (s, 2H, OH), 7.14 (d, J＝8.7 Hz, 2H, ArH), 7.05~6.90 (m, 12H, ArH), 6.85 (s, 2H, ArH), 6.79 (d, J＝7.7 Hz, 4H, ArH), 6.67 (s, 2H, ArH), 6.30 (s, 2H, CH＝N), 6.25 (dd, J＝8.6, 2.4 Hz, 2H, ArH), 6.20 (d, J＝2.2 Hz, 2H, ArH), 4.49 (s, 4H, CH₂), 4.30 (d, J＝7.7 Hz, 2H, NH), 4.10 (s, 2H, CH₂), 4.02~3.48 (m, 66H, 48OCH₃, 18CH₂), 3.41 (s, 6H, CH₂), 3.24 (s, 6H, CH₂), 1.81 (t, J＝7.6 Hz, 8H, CH₂), 1.51 (dq, J＝14.0, 7.3 Hz, 8H, CH₂), 1.37 (s, 8H, CH₂), 0.98 (t, J＝7.4 Hz, 6H, CH₃), －0.15 (dd, J＝20.0, 11.4 Hz, 4H, CH₂), －1.73 (s, 2H, CH₂), －1.90 (s, 2H, CH₂); ¹³C NMR (101 MHz, CDCl₃) δ: 170.33, 166.79, 164.30, 163.78, 163.20, 162.30, 151.45, 150.84, 150.54, 150.50, 150.19, 150.13, 149.69, 148.53, 132.86, 132.51, 131.68, 129.84, 129.21, 128.54, 128.44, 128.16, 127.84, 127.77, 126.49, 125.83, 118.02, 114.12, 113.92, 113.59, 113.36, 113.21, 112.38, 112.23, 112.12, 112.09, 111.44, 106.86, 105.64, 101.86, 101.71, 77.37, 70.34, 68.07, 67.90, 65.93, 56.11, 55.95, 55.72, 55.61, 55.44, 55.19, 55.03, 50.88, 36.09, 32.05, 31.92, 30.09, 29.58, 29.50, 29.47, 29.41, 29.36, 29.22, 29.20, 29.08, 28.63, 28.61, 28.17, 27.01, 26.12, 26.08, 26.00, 19.47, 14.06; IR (KBr) v: 3397, 2933, 1683, 1626, 1500, 1465, 1399, 1297, 1213, 1045, 928, 880, 775, 703, 648 cm^－1; HRMS (ESI) calcd for C₁₂₈H₁₅₄N₄O₂₆ ([M+H]⁺): 2165.0966, found 2165.0958.

辅助材料(Supporting Information) 化合物3a~3h的HRMS、¹H NMR和¹³C NMR图谱.这些材料可以免费从本刊网站(http://sioc-journal.cn/)上下载.

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图 1 双[1]轮烷3a的核磁氢谱部分图(400 MHz, 298 K, CDCl₃)

Figure 1 Partial ¹H NMR spectrum (400 MHz, 298 K, CDCl₃) of bis-[1]rotaxane 3a

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图 2 双[1]轮烷3a的¹H-¹H NOESY图谱(600 MHz, 298K, CDCl₃)

Figure 2 ¹H-¹H NOESY spectrum (600 MHz, 298 K, CDCl₃) of bis-[1]rotaxane 3a

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图式 1 双-[1]轮烷3a~3h合成路线

Scheme 1 Synthesis of bis-[1]rotaxane 3a~3h

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图 3 双[1]轮烷3a与不同金属离子的紫外吸收图

Figure 3 Ultraviolet absorption diagram of bis-[1]rotaxane 3a and different metal ions

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图 4 双[1]轮烷3a与不同浓度的Cu²⁺离子的络合比曲线

Figure 4 Complex ratio curve of bis-[1]rotaxane 3a with differ- rent concentrations of Cu²⁺

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表 1 8个双[1]轮烷产率及核磁对比

Table 1. Yields of bis[1]rotaxanes and their difference on ¹H NMR

Compd.	n	m	Yield/%	Number of H (δ＜0)
3a	4	1	66.5	16 (CH₂)
3b	4	2	54.6	16 (CH₂)
3c	2	1	83.4	8 (CH₂)
3d	2	2	65.3	8 (CH₂)
3e	2	4	64.3	8 (CH₂)
3f	1	1	81.1	8 (CH₂)
3g	1	2	65.2	8 (CH₂)
3h	1	4	52.6	8 (CH₂)

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