CN109305926B - 一种可形成分子内氢键的芳酰胺类金属配体及其制备方法与应用 - Google Patents

一种可形成分子内氢键的芳酰胺类金属配体及其制备方法与应用 Download PDF

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CN109305926B
CN109305926B CN201811214558.4A CN201811214558A CN109305926B CN 109305926 B CN109305926 B CN 109305926B CN 201811214558 A CN201811214558 A CN 201811214558A CN 109305926 B CN109305926 B CN 109305926B
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dimethoxy
isophthalamide
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王力彦
刘悦
邢珮琪
裘令瑛
李豹
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Abstract

本发明提出了一种可形成分子内氢键的芳酰胺类金属配体及其制备方法与应用，本发明属于配位聚合物材料技术领域。针对目前有些配体在形成配位聚合物晶体时其分子构象具有多样性因而难以预测的问题，本发明根据分子内氢键在限制分子内旋转的作用提出可形成分子内氢键的配体，能够通过氢键抑制配体分子内旋转，在形成晶体时能够得到配体的特定构象，解决了该技术问题。

Description

一种可形成分子内氢键的芳酰胺类金属配体及其制备方法与 应用
技术领域
本发明属于配位聚合物材料技术领域。
背景技术
配位聚合物由于其在催化、气体分离、离子交换、磁性等方面的应用，吸引了科学家的广泛关注。其结晶过程本身是一个动态的自组装过程，发展新的预测和控制配位聚合物晶体结构的方法是非常有意义的。晶体工程中，刚性配体在合成晶体时能够实现对结构良好的预测，组装成有特定拓扑和功能的结构，可形成具有永久孔隙的金属有机框架；柔性配体与刚性配体相比在自组装过程中很容易扭曲和旋转，产生结构多样性，同时晶体中的孔常常属于可收缩和膨胀的动态多孔。
折叠体由于在分子识别、运输、电子转移和催化上的应用，受到了极大的关注。黎占亭等人的综述中总结了一些含氢键的折叠体，氢键的存在限制了构象的自由旋转，使原本柔性的配体具有一定的刚性，形成折叠、螺旋的构象。
分子内氢键在限制分子内旋转上起了很大的作用，但在目前的研究中几乎没有看到晶体中配体自身可形成氢键控制旋转的，因此本发明提出可形成分子内氢键的配体，能够通过氢键抑制配体分子内旋转，在形成晶体时能够得到配体的特定构象。
发明内容
为了解决上述问题，本发明提出了一种以可形成分子内氢键的配体来解决配位聚合物形成晶体时会产生多种结构的技术问题。
本发明中所提供的可形成分子内氢键的芳酰胺类金属配体的结构如下：
Figure GDA0001886849400000011
其中，R代表C-COOH或N，
即：
Figure GDA0001886849400000012
命名：4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺和
Figure GDA0001886849400000021
命名：4,6-二甲氧基-N,N’-二(吡啶-4-基)间苯二甲酰胺。
所述的可形成分子内氢键的芳酰胺类金属配体的制备方法如下：
在圆底烧瓶中加入0.8～1.2mmol 4，6-二甲氧基间苯二甲酸，再加入5～8mmol乙二酰氯、10～15mL二氯甲烷、1～2滴DMF，室温反应0.5～1h，再加热回流1～2h，抽干溶剂，得到4，6-二甲氧基间苯甲二酰氯。将4，6-二甲氧基间苯二甲酰氯的20～40mL DMA溶液，逐渐滴加到含有8mmol对氨基苯甲酸或4-氨基吡啶，以及0.4～0.6mL三乙胺的20～40mL DMA溶液中，室温搅拌16～24h。加入大量的水析出沉淀，抽滤。沉淀依次用丙酮、水和甲醇洗涤后，室温干燥，得到可形成分子内氢键的芳酰胺类金属配体，4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺或4,6-二甲氧基-N,N’-二(吡啶-4-基)间苯二甲酰胺。
所述的可形成分子内氢键的芳酰胺类金属配体用于制备配位聚合物的用途。
制备配位聚合物的方法有如下四种：
1)将六水合硝酸钴(0.025～0.035mmol，7.25～10.15mg)与4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺(0.025～0.035mmol，11.58～16.22mg)混合在3.5～4.5mLDMF中，80℃保持80～90h，得到紫色透明的菱形晶体；或将六水合氯化钴(0.025～0.035mmol，5.95～8.33mg)与4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺(0.025～0.035mmol，11.58～16.22mg)混合在4.5～5.5mL DMF/EtOH(体积比4:1)的混合液中，80℃保持80～90h，也可得到紫色透明的菱形晶体。
2)将四水合硝酸镉(0.025～0.035mmol，7.67～10.73mg)与4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺(0.025～0.035mmol，11.58～16.22mg)混合在5.5～6.5mLDMA/MeOH(体积比2:1)的混合溶液中，80℃保持80～90h，得到无色透明的菱形晶体。
3)将六水合硝酸锌(0.025～0.035mmol，5～7mg),4,4’-联吡啶(0.03～0.04mmol，4.62～6.16mg)与4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺(0.025～0.035mmol，11.58～16.22mg)混合在5.5～6.5mL DMF/H2O(体积比2:1)的混合液中，70℃保持80～90h，得到晶体和沉淀的混合液，用大量DMF洗3～5次，得到无色透明的菱形晶体。
4)将硝酸银(0.025～0.035mmol，4.25～5.95mg)、对苯二甲酸(0.025～0.035mmol，4.15～5.83mg)与4,6-二甲氧基-N,N’-二(吡啶-4-基)间苯二甲酰胺(0.025～0.035mmol，9.46～13.24mg)混合在4～5mL DMA/MeOH(体积比2:1)的混合溶液中，80℃保持80～90h，得到黄棕色透明的长方形晶体。
附图说明
图1～图3为晶体1的结构；
图4～图6为晶体4的结构；
图7为L1上的芳香环的编号；
图8为L2上的芳香环的编号；
图9本发明中L1的1H-NMR(d6-DMSO)谱图；
图10本发明中L1的13C-NMR(d6-DMSO)谱图；
图11本发明中L2的1H-NMR(d6-DMSO)谱图；
图12本发明中L2的13C-NMR(d6-DMSO)谱图；
图13本发明晶体1的红外光谱图；
图14本发明晶体2的红外光谱图；
图15本发明晶体3的红外光谱图；
图16本发明晶体4的红外光谱图；
图17本发明晶体1的粉末衍射图(下方的线为实际测出来的，上方的线是预测出的结果)；
图18本发明晶体2的粉末衍射图(上方的线为实际测出来的，下方的线是预测出的结果)；
图19本发明晶体3的粉末衍射图(上方的线为实际测出来的，下方的线是预测出的结果)；
图20本发明晶体4的粉末衍射图(上方的线为实际测出来的，下方的线是预测出的结果)；
具体实施方式
下面以具体实施例的形式对本发明技术方案做进一步解释和说明。
实施例1
在圆底烧瓶中加入1mmol 4，6-二甲氧基间苯二甲酸，再加入6.9mmol乙二酰氯、10mL二氯甲烷、1-2滴DMF，室温反应0.5h，再加热回流90min，抽干溶剂，得到4，6-二甲氧基间苯甲二酰氯。将4，6-二甲氧基间苯二甲酰氯的20mL DMA溶液，逐渐滴加到含有8mmol对氨基苯甲酸、0.49mL三乙胺的20mL DMA溶液中，室温搅拌16h。加入大量的水析出沉淀，抽滤。沉淀依次用丙酮、大量的水、甲醇洗，室温干燥，得到L1。
如图9，1H NMR(DMSO):δ12.73(s,2H),10.28(s,2H),8.15(s,1H),7.94(d,J＝8.7Hz,4H),7.87(d,J＝8.7Hz,4H),6.91(s,1H),4.08(s,6H).
如图10，13C NMR(DMSO):δ167.40(s),163.97(s),161.07(s),143.39(s),133.47(s),130.81(s),125.90(s),119.65(s),116.57(s),97.00(s),57.25(s)。
实施例2
在圆底烧瓶中加入1mmol 4，6-二甲氧基间苯二甲酸，再加入6.9mmol乙二酰氯、10mL二氯甲烷、1-2滴DMF，室温反应0.5h，再加热回流90min，抽干溶剂，得到4，6-二甲氧基间苯甲二酰氯。将4，6-二甲氧基间苯二甲酰氯的20mL DMA溶液，逐渐滴加到含有8mmol 4-氨基吡啶、0.49mL三乙胺的20mL DMA溶液中，室温搅拌16h。加入大量的水析出沉淀，抽滤。沉淀用大量的水洗，真空干燥，得到L2。
如图11，1H NMR(DMSO)：δ10.31(s,2H),8.47(d,J＝6.2Hz,4H),8.10(s,1H),7.73(d,J＝6.3Hz,4H),6.91(s,1H),4.07(s,6H).
如图12，13C NMR(DMSO):δ164.60(s),161.27(s),150.82(s),145.94(s),133.37(s),116.39(s),114.30(s),97.03(s),57.28(s).
实施例1和实施例2中，合成4，6-二甲氧基间苯二甲酸(S4)的方法可以参考文献(J.Am.Chem.Soc.,2014,136,12119-12129；Chin.Chem.Lett.,2005,16,1039-1042；J.Am.Chem.Soc.,2000,122,2635-2644；J.Org.Chem.,2005,70,10660-10669；PNAS,106,17,6968-6973；Angew.Chem.Int.Ed.,2015,54,11117-11121；Chem.Commun.,2012,48,2228-2230)。
合成路线如下：
Figure GDA0001886849400000041
实施例3
晶体1的制备：将六水合硝酸钴(0.03mmol，8.7mg)与L1(0.03mmol，13.9mg)混合在4mL DMF中，80℃保持90h，得到紫色透明的菱形晶体。
另外，用六水合氯化钴(0.03mmol，7.14mg)与L1(0.03mmol，13.9mg)混合在5mLDMF/EtOH(体积比4:1)的混合液中，80℃保持90h，也可得到紫色透明的菱形晶体。
晶体2的制备：将四水合硝酸镉(0.03mmol，9.2mg)与L1(0.03mmol，13.9mg)混合在6mL DMA/MeOH(体积比2:1)的混合溶液中，80℃保持90h，得到无色透明的菱形晶体。
晶体3的制备：将六水合硝酸锌(0.03mmol，6mg),4,4’-联吡啶(0.039mmol，6mg)与L1(0.03mmol，13.9mg)混合在6mL DMF/H2O(体积比2:1)的混合液中，70℃保持90h，得到晶体和沉淀的混合液，用大量DMF洗5次，得到无色透明的菱形晶体。
晶体4的制备：将硝酸银(0.03mmol，5.1mg)、对苯二甲酸(0.03mmol，4.98mg)与L2(0.03mmol，11.35mg)混合在4.5mL DMA/MeOH(体积比2:1)的混合溶液中，80℃保持90h，得到黄棕色透明的长方形晶体。
晶体结构的表征
单晶X射线衍射数据是在衍射仪(采用石墨单色器，用Mo Kα射线
Figure GDA0001886849400000052
)上测定的。数据还原和解析工作是用SHELXTL-97和Olex2完成的。表1是四个晶体的晶体学数据。
表1四个晶体的晶体学数据
Figure GDA0001886849400000051
Figure GDA0001886849400000061
晶体1属于单斜晶系P21/c空间点群，不对称单元中含2个配体分子L1、2个钴离子和2个DMF分子，如图1。不对称单元在一起组成了一个网格结构，如图2所示。同层间三个网格等距交错贯穿排列，相互套在一起，像编织的大网一样，如图3是晶体的穿插式样。在这三个晶体中，配体分子L1均采用同一种构象，配体中间的苯环上的烷氧基与酰胺键的N-H形成分子内氢键，说明氢键的存在限制了芳酰胺的旋转，使得分子获得一个比较刚性的结构。分子内存在氢键使得L1的两个羧基呈现139.29°夹角，沿着a轴和b轴形成了波浪形长链。晶体2和晶体3的结构与晶体1的十分相似。晶体2的不对称单元中含2个配体分子L1、2个镉离子、2个DMA分子和游离的甲醇。分子内存在氢键使得L1的两个羧基呈现139.03°夹角。晶体3的不对称单元中含2个配体分子L1、2个锌离子和2个DMF分子。分子内存在氢键使得L1的两个羧基呈现137.90°夹角。
晶体1中钴离子采用扭曲的六配位结构，其中四个配位点与L1的四个羧基O配位，一个与DMF中的O配位，还有一个与Co形成金属键。每个羧基的两个O原子连接着两个金属原子。晶体1中钴与L1和DMF上的氧原子配位的Co-O键长在
Figure GDA0001886849400000062
之间，钴与其配位的原子的键角83.74-162.89°之间(表2)。配体分子中氢键N2-H2…O5的距离为
Figure GDA0001886849400000063
N1-H1…O4的距离为
Figure GDA0001886849400000064
晶体是以Co-Co键的中心作为对称中心的中心对称结构。层间距离为
Figure GDA0001886849400000065
存在C-H…O的氢键相互作用。
表2晶体1的关键键长和键角
Figure GDA0001886849400000071
晶体2中镉离子采用扭曲的五配位结构，其中四个配位点与配体的四个羧基O配位，一个与DMA中的O配位。每个羧基两个O原子连接着两个金属原子。晶体2中镉金属与L1和DMA上的氧原子配位的Cd-O键长在
Figure GDA0001886849400000073
之间，镉与其配位的原子的键角86.08-158.43°之间(表3)。配体分子中氢键N2-H2…O5的距离为
Figure GDA0001886849400000074
N1-H1…O4的距离为
Figure GDA0001886849400000075
晶体是以两个Cd金属原子连线的中点作为对称中心的中心对称结构。层间距离为
Figure GDA0001886849400000076
存在C-H…π相互作用。
表3晶体2的关键键长和键角
Figure GDA0001886849400000072
晶体3中锌离子采用扭曲的五配位结构，其中四个配位点与配体的四个羧基O配位，一个与DMF中的O配位。每个羧基两个O原子连接着两个金属原子。晶体3中锌与L1和DMF上的氧原子配位的Zn-O键长在
Figure GDA0001886849400000085
之间，锌与其配位的原子的键角85.863-160.283°之间(表4)。配体分子中氢键N2-H2…O5的距离为
Figure GDA0001886849400000086
N1-H1…O4的距离为
Figure GDA0001886849400000087
晶体是以两个Zn金属原子连线的中点作为对称中心的中心对称结构。层间距离为
Figure GDA0001886849400000088
存在C-H…O氢键相互作用。
表4晶体3的关键键长和键角
Figure GDA0001886849400000081
晶体4属于单斜晶系C c空间点群，不对称单元中含1个L2，一个金属离子，1个对苯二甲酸分子，还存在游离的甲醇，如图4。不对称单元在一起组成了一个网格结构，如图5所示。晶体中配体分子L2中间的苯环上的烷氧基与酰胺键的N-H形成分子内氢键，氢键的存在限制了芳酰胺的旋转，使L2获得一个比较刚性的结构。同层间三个网格等距交错贯穿，不同网格之间相互套在一起，如图6。层间排列模式是AAA模式。晶体4中银采用四配位模式，其中两个配位点与L2的吡啶环N配位，两个配位点与对苯二甲酸上的O配位，键长与键角如表5。表5晶体分子中氢键N3-H3…O7的距离为
Figure GDA0001886849400000083
N2-H2…O6的距离为
Figure GDA0001886849400000084
表5晶体4的关键键长和键角
Figure GDA0001886849400000082
Figure GDA0001886849400000091
晶体1-晶体4的红外光谱图如图13～图16，粉末XRD数据如图17～图20。
将配体上芳香环编号①②③，如图7。测量了芳香环之间的二面角，结果如表6所示。可以看出，在四个晶体中配体芳香环间的二面角均小于10°，说明配体的氢键很好地控制了构象的变化，而且配体分子的构象是平面型。
表6配体芳香环间的二面角
Figure GDA0001886849400000092
综上所述，本发明实施例中制备出不同于以往的可形成分子内氢键的配体L1和L2。将其用于配位化合物的制备中，在四个晶体中配体芳香环间的二面角均小于10°，说明含有分子内氢键的配体的构象灵活性下降，在晶体中只发现一种最优构象。

Claims (7)

1.一种可形成分子内氢键的芳酰胺类金属配体，其特征在于，该配体的分子结构如下：
Figure FDA0002832968160000011
其中，R代表C-COOH或N，当R代表C-COOH时，分子式为
Figure FDA0002832968160000012
命名为4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺；
当R代表N时，分子式为
Figure FDA0002832968160000013
命名为4,6-二甲氧基-N,N’-二(吡啶-4-基)间苯二甲酰胺。
2.如权利要求1所述的可形成分子内氢键的芳酰胺类金属配体的制备方法，具体步骤如下：
在圆底烧瓶中加入0.8～1.2mmol 4，6-二甲氧基间苯二甲酸，再加入5～8mmol乙二酰氯、10～15mL二氯甲烷、1～2滴DMF，室温反应0.5～1h，再加热回流1～2h，抽干溶剂，得到4，6-二甲氧基间苯甲二酰氯；将4，6-二甲氧基间苯二甲酰氯的20～40mL DMA溶液，逐渐滴加到含有8mmol对氨基苯甲酸或4-氨基吡啶，以及0.4～0.6mL三乙胺的20～40mL DMA溶液中，室温搅拌16～24h；加入大量的水析出沉淀，抽滤；沉淀依次用丙酮、水和甲醇洗涤后，室温干燥，得到可形成分子内氢键的芳酰胺类金属配体，4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺或4,6-二甲氧基-N,N’-二(吡啶-4-基)间苯二甲酰胺。
3.如权利要求1所述的可形成分子内氢键的芳酰胺类金属配体用于制备配位聚合物的用途。
4.根据权利要求3所述的可形成分子内氢键的芳酰胺类金属配体的用途，其特征在于，制备配位聚合物的具体步骤如下：
将0.025～0.035mmol六水合硝酸钴与0.025～0.035mmol 4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺混合在3.5～4.5mL DMF中，80℃保持80～90h，得到紫色透明的菱形晶体；或将0.025～0.035mmol六水合氯化钴与0.025～0.035mmol 4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺混合在4.5～5.5mL DMF/EtOH的混合液中，80℃保持80～90h，得到紫色透明的菱形晶体，其中，DMF与EtOH体积比为4:1。
5.根据权利要求3所述的可形成分子内氢键的芳酰胺类金属配体的用途，其特征在于，制备配位聚合物的具体步骤如下：
将0.025～0.035mmol四水合硝酸镉与0.025～0.035mmol 4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺混合在5.5～6.5mL DMA/MeOH的混合溶液中，80℃保持80～90h，得到无色透明的菱形晶体，其中，DMA与MeOH体积比为2:1。
6.根据权利要求3所述的可形成分子内氢键的芳酰胺类金属配体的用途，其特征在于，制备配位聚合物的具体步骤如下：
将0.025～0.035mmol六水合硝酸锌、0.03～0.04mmol 4,4’-联吡啶与0.025～0.035mmol 4,6-二甲氧基-N,N’-二(4-羧基苯基)间苯二甲酰胺混合在5.5～6.5mL DMF/H2O的混合液中，70℃保持80～90h，得到晶体和沉淀的混合液，用大量DMF洗3～5次，得到无色透明的菱形晶体；其中，DMF与H2O的体积比为2:1。
7.根据权利要求3所述的可形成分子内氢键的芳酰胺类金属配体的用途，其特征在于，制备配位聚合物的具体步骤如下：
将0.025～0.035mmol硝酸银、0.025～0.035mmol对苯二甲酸与0.025～0.035mmol 4,6-二甲氧基-N,N’-二(吡啶-4-基)间苯二甲酰胺混合在4～5mL DMA/MeOH的混合溶液中，80℃保持80～90h，得到黄棕色透明的长方形晶体；其中，DMA与MeOH的体积比为2:1。
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