CN104945342A - 一种含氮杂环羧酸类配体及制备方法 - Google Patents
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Abstract
<b/><b/>本发明公开一种功能配体及制备方法，具体方法如下：(1)1-20mmoL对氰基苯甲酸、1-80mmoL水合肼和1-35mmoL乙二醇相互混合放入反应釜中。（2）将步骤1放入电热鼓风机中，设置温度范围为50度-160度之间，加热1-7天后缓慢降至室温。（3）将步骤2得到的产品边搅拌边加入1-100mL水后，在滴加无机酸1-10mL调整溶液的pH为1-4。(4)产品抽滤、干燥，得到产品命名为44CA。(2)44CA的化学式为C16H12N4O4，所述配体为斜方晶系，Pbcm空间群，晶胞参数为a=3.7674(9)?，b=11.271(3)?，c=33.244(9)?，α=90°，β=90°，γ=90°，V=1411.7(6)?3。本发明提供一种既含氮杂环又含羧基酸双官能团的新型配体的合成方法。这类配体为具有新型结构和特殊性质的金属配位聚合物的合成提供了更多可能。本发明达到了简化实验操作，一步合成出目标配体。
Description
技术领域
本发明属于化学合成领域，涉及到一种有机配体的合成方法，其主要目的用于制备金属有机配位聚合物，属于功能材料领域。
背景技术
众所周知，有机配体在构筑新颖配合物起重要作用。有机配体含有的配原子的种类，可对不同的金属离子产生不同的亲和作用，且配原子之间的角度会影响配体中参与配位的原子数目的多少，并决定配体的连接方式。正是由于有机配体中配原子的这种导向作用，使得 N、O、S 等具有较强供电子能力的原子成为适合的配原子，而含有氮杂环、羧基、胺基、磺酸基、硫杂环等结构片段的有机配体自然也就成为构筑配位聚合物的研究热点。
迄今为止，含氮杂环羧酸类配体它兼具含氮杂环和羧酸类配合物的优点，是典型的多功能有机配体，可以和许多金属粒子形成结构新颖的多孔配合物，近些年来受到越来越多的关注。含碳杂环羧酸类配体所具有的特点：（1）不同pH 值下可部分或全部去质子化，与金属中心产生不同形式、不同程度的配位，同时可以作为氢键受体和供体。（2）该类配体同时含有 N、O 原子具有较强的配位能力，配位模式多样，和金属离子配位能形成稳定的四元环、五元环和七元环。(3)含氮杂环上的羧基是可以自由旋转，这有助于形成新颖的螺旋链或手性结构。通过以上特点，它们在参与配位时具有很大的协同效应和对称性，容易形成中心对称的配合物，并且氮原子与羧基和金属离子配位时的配位能力和选择性不同，往往可以得到多种结构新颖、性能优异的配位聚合物。(Z. Y. Li, Z. M. Zhang, J. W. Dai, [J]. J. Mol. Struct., 2010, 963, 50-56)。
发明内容
本发明提供一种含有含氮杂环羧酸类配体的合成方法，结合了含 N 杂环配体和含 O 羧酸配体的优点。这类配体由于其具有不同功能的给体原子 N和O，所以具有较丰富的配位形式和较强的配位能力，为功能配位聚合物的设计和构筑提供了更多可能，本发明达到了简化实验操作步骤，达到一步合成的目的。
为了实现本发明的目的，主要是通过溶剂热反应获得了一种即有含 N 杂环配体又含有羧酸的功能配体。配体的优点在于具有潜在配位功能的44CA配体。
本发明主要采取以下技术方案：（1）将1—20mmoL对氰基苯甲酸，1—80mmoL水合肼和1—35mmoL乙二醇三者相互混合，放入聚四氟乙烯的反应釜。（2）将反应釜放入GZX—9030MBE电热鼓风机中，设置温度范围为50度—160度之间（优选130度），加热1—7天（优选3天）。（3）加热1—7天后，以每小时5度的速率降温，至其降到室温温度，加入1—100mL水后，搅拌边滴加再加入无机酸（盐酸，硫酸，硝酸，高氯酸，磷酸，四氟硼酸）1—10mL调整溶液的pH为1—4之间。（4）将得到的产品进行抽滤，自然晾干后得到这个功能配体，命名为44CA。
本发明的有益效果：结合了含 N 杂环配体和含 O 羧酸配体的优点，配体由于其具有不同功能的给体原子 N和O，所以具有较丰富的配位形式和较强的配位能力，为具有特殊结构和 性能的金属配位聚合物的合成和制备提供了更多可能，而所得的功能配体中的共轭单元为配位聚合物的显色或荧光发色提供了条件。
附图说明
图1、44CA的分子结构图。
图2、44CA的一维链图。
图3、44CA的二维层图。
图4、44CA的堆积图。
图5、44CA的红外谱图。
图6、44CA的荧光谱图。
具体实施方式
将得到的44CA进行重结晶进行提纯，主要是通过水热合成得到44CA本身的晶体，根据0.05—0.15mmol 44CA与1—20 mL水相互混合后，并且滴加1—4滴无机酸（盐酸，硫酸，硝酸，高氯酸，磷酸，四氟硼酸）(优选硫酸)放入聚四氟乙烯反应釜，将反应釜放入GZX—9030MBE电热鼓风机中。设置温度范围为50度—200度之间，加热1—7天后过滤后的到44CA本身的晶体。
通过单晶结构衍射、傅里叶红外光谱表征手段对重结晶后的44CA进行了结构表征。另外测量其的荧光性质。正如图5所示，配体中特征峰为3363nm；1629nm；1290nm；783nm。配体中含有三唑的π…π堆积表现出了荧光特性，在图6中可以看到其发射光谱为271nm。
图1是由单晶衍射方法得到44CA结构。该混合配体的配位聚合物的X射线衍射数据是在 Bruker smart Apex CCD面探衍射仪上,用MoKa辐射,以w扫描方式收集并进行Lp因子校正,吸收校正使用SADABS是程序。用直接法解结构,然后用差值傅立叶法求出全部非氢原子坐标,并用理论加氢得到氢原子位置。用最小二乘法对结构进行修正，计算工作在PC机上用SHELXTL程序包完成。配体晶体学参数见表1
表1.配体的晶体学参数
在44CA配体结构中，该分子中含有一个三氮唑和一个氨基和两个4－羧基苯构成。在三氮唑的N2原子上连接一个氨基，在三氮唑的C8原子和另一个C8原子上分别连接着4－羧基苯。
图2所示01—H(1)…02氢键的形成。44CA配体上中的一个苯甲酸的羧基氧与另一个配体上的羧基氧01—H(1)…02（2.643(3) ?）形成了一种分子间氢键，通过该氢键作用形成了一维超分子链状结构。
图3为44CA配体中存在另外一种氢键。该氢键是由氨基上的氮原子和三氮唑上的氮原子构筑而成N1—H(3A)…N3（3.176(4) ? ），形成了沿着晶胞b轴的氢键，而图2中的O1—H…O2氢键是沿着晶胞c轴连接而成，通过这两种氢键相互作用从而形成一个二维超分子层结构。
图4为44CA分子堆积图。44CA配体中存在两种π…π堆积作用。一种是44CA配体中苯环的π…π键相互堆积（3.7674(18) ?），另一种是44CA配体中三氮唑环的π…π键相互堆积作用（3.7675(17) ?），这两种堆积作用进一步把图2中的二维层扩展成一个三维超分子体系。
图6为44CA的室温固态荧光光谱图。正如图6所示，在激发波长为271nm时，化合物44CA在399nm位置处出现了最大发射峰，这可归属于配体π*→π的电子迁移所致。
Claims (7)
1.一种功能配体指的是同时含有含氮杂环和羧酸两种官能团的配体。44CA的化学式为C16H12N4O4，配体为斜方晶系，Pbcm空间群，晶胞参数为a=3.7674(9)?，b=11.271(3)?，c=33.244(9)?,α=90°，β=90°，γ=90°，V=1411.7(6) ?3。其所示的化学结构：
(1)实施例1、化合物44CA的合成
将对氰基苯甲酸溶于适量有机溶剂，并逐渐滴加水合肼，然后将反应混合液转入反应釜中加热完成后，至其降到室温,加入适量的水后并加入适量的无机酸得到沉淀后，进行抽滤操作后自然晾干得到目标产物44CA，并将所得固体化合物加入适当的溶剂进行水热合成，设置适当的温度和时间得到44CA晶体，44CA的结构经IR,单晶X-射线衍射确认，并由单晶X-射线衍射确定其晶体结构。
2.根据权利要求书1所述的功能配体的合成方法，其特征在于所选的有机溶剂为含碳原子数为1-10的单醇、双醇、三醇、四醇或多羟基醇、丙酮、乙酸乙酯、二甲基亚砜、N,N-二甲基甲酰胺、二氯甲烷、三氯甲烷、四氯化碳、硝基甲烷、四氢呋喃、N－甲基吡咯烷酮、石油醚、苯、甲苯的单一溶剂或混合溶剂。
3.根据权利要求书1所述的功能配体的合成方法，其特征在于所选的无机溶剂为盐酸，硫酸，硝酸，高氯酸，磷酸,四氟硼酸。
4.根据权利要求书1所述的功能配体的合成方法，其特征在对氰基苯甲酸与有机溶剂的比例为1：1-3。
5.根据权利要求书1所述的功能配体的合成方法，其特征在对氰基苯甲酸与水合肼的比例为1：1-5。
6.根据权利要求书1所述的功能配体的合成方法，其特征在于所选的温度范围为从50到200摄氏度。
7.根据权利要求书1所述的功能配体的合成方法，其特征在于所反应的时间范围为1到7天。
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