CN108912342A - 一种一维链3,5-二硝基水杨酸2,2’-联吡啶锰(ii)配位聚合物 - Google Patents
一种一维链3,5-二硝基水杨酸2,2’-联吡啶锰(ii)配位聚合物 Download PDFInfo
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- -1 dinitrosalicylic acid manganese (II) Chemical compound 0.000 title claims abstract description 27
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 22
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 21
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 9
- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000006243 chemical reaction Methods 0.000 claims description 7
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- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
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- C08G83/008—Supramolecular polymers
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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Abstract
本发明提供一种新的一维链3,5‑二硝基水杨酸2,2’‑联吡啶锰(II)配位聚合物的晶体结构及晶体学参数。该配合物以3,5‑二硝基水杨酸,2,2’‑联吡啶为配体，以过渡金属锰为中心离子，通过配位键合组装成具有一维链3,5‑二硝基水杨酸2,2’‑联吡啶锰(II)配位聚合物。
Description
技术领域
本发明涉及功能材料、功能配合物、晶体学领域，特别是涉及一种新的一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物及其制备方法。
背景技术
金属有机框架(metal-organic frameworks，MOFs)材料是一类由有机配体与金属中心经过自组装形成的具有可调节孔径的材料。与传统无机多孔材料相比，MOFs材料具有更大的比表面积，更高的孔隙率，结构及功能更加多样，因而已经被广泛应用于气体吸附与分离、传感器、药物缓释、催化反应等领域中,在非线性光学材料、磁性材料、超导材料等诸多方面显示出极好的应用前景。利用有机桥联配体与金属离子组装获得可以预测固体材料的几何结构，其中配位键或氢键、π-π芳环堆积弱相互作用、静电作用和空间支撑作用在调控MOF拓扑结构和性能方面具有非常重要的作用。卤代芳酸、4,4,–联吡啶等桥联配体能够跟多种金属组装成一维、二维和三维超分子，有关非线性光学性能、催化作用、光电转换性能的研究成果已见报道。
自1967年顺铂的首次抗肿瘤活性被发现并应用于临床以来，使得金属配合物的抗肿瘤活性研究倍受人们的关注。人们不断地设计并且合成出具有新颖结构的配合物，并进行筛选，希望能从中得到具有高效、低毒、高选择性的抗肿瘤药物。吡啶多羧酸类配体具有多种的配位基团，能以多样方式与金属发生配位作用，因此其配位聚合物的研究也受到学者的广泛关注。有研究者以4-羟基吡啶2,6-二甲酸为配体，依据晶体学原理，利用水热法成功合成了以下6个具有多种新颖结构的过渡金属以及稀土金属配位聚合物，并得到了单晶：(1)Nd(CAM)(H2O)3·H2O,(2)Cd4(HCAM)4(H2O)8,(3)La2(CAM)2(H2O)6,(4)Sm(CAM)(H2O)3·H2O,(5)Ce2(CAM)2(H2O)6,(6)Mn4(CAM)3·H3O.运用X-单晶衍射分析法进行了结构测定，并对配合物晶体结构进行简要的描述。测定了红外光谱，对配合物和配体的红外光谱进行了经验归属，对配合物和配体的固体荧光进行简要的性质研究，配体及配合物(1)(2)(3)(4)都表现出荧光特性。运用MTT法，检测配合物对K562细胞、HL60细胞的抑制作用，结果表明配合物2对两株细胞均具有一定的细胞毒性作用。而配合物1、6只对HL60细胞表现出活性抑制作用。说明吡啶羧酸类金属配合物可能具有抗肿瘤活性；.
陈振锋等人运用5-硝基-8-羟基喹啉、5-溴-8-羟基喹啉、5-氨基-8-羟基喹啉和Co(NO3)2·6H2O在乙醇-水体系中，吡啶调节反应溶液pH，反应得到3个Co配合物3a-3c，该系列化合物对所选的肿瘤细胞株表现出比配体强的细胞毒性，其中对T-24膀胱癌细胞的毒性最大，IC50在7.00-16.70μM，而顺铂对T-24的IC50为15.93。初步的作用机制研究表明，3a把细胞阻滞在G1期，诱导活性氧(ROS)过表达，使线粒体膜电位下降，激活caspase-3、caspase-9,推测配合物可能通过线粒体通路诱导肿瘤细胞凋亡。
JEEWOTH等人用2,3-二氨基吡啶分别与水杨醛、4-羟基苯甲醛及硝基苯甲醛合成了相应的Cu(Ⅱ)、Zn(Ⅱ)、Ni(Ⅱ)Schiff碱金属配合物，同时合成了一种不同醛混合组成的Schiff碱配体2,3-二氨基吡啶缩4-羟基苯甲醛-水杨醛及相应金属配合物，且具有一定的选择性抗菌活性。GOYAL等用5-硝基-2-苯甲醛及2-羟基-5氯苯甲醛与磺胺二甲异唑和黄胺甲氧哒嗪(SMP)合成了相应的Schiff碱及Mn(Ⅱ)、Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)和Cu(Ⅱ)配合物，结果发现配合物较配体有更高的抗真菌活性，其中Cu(Ⅱ)配合物的抗真菌活性最高。
饶小平等人合成了一系列的脱氢枞胺(5-硝基)水杨醛Schiff碱及其Cu(Ⅱ)、Zn(Ⅱ)、Co(Ⅱ)和Ni(Ⅱ)配合物。同时，对这些配体及配合物进行了抑制大肠杆菌、金黄色葡萄球菌及枯草芽孢杆菌的生物活性测定，配体及配合物都表现出一定的生物活性。其中，Cu(Ⅱ)的生物活性较高，能够用于治疗由这些细菌引起的各种疾病，且具有低毒，选择性高等优点。
鉴于金属配合物在医药领域的广泛应用，设计和合成一些新型的金属配合物成为目前亟待解决的技术问题。
发明内容
本发明的一个目的是提供一种新的一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物的晶体结构及晶体学参数。该配合物以3,5-二硝基水杨酸,2,2’-联吡啶为配体，以过渡金属锰为中心离子，通过配位键合组装成具有一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物。为了实现上述的第一个目的，本发明采用了以下的技术方案：
一种一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物，其晶体学数据如下：
其中，在本发明一个优选地实施方式中，Mn---N的键长为2.2245(17),和Mn---O键的键长范围在之间，相邻键角范围在55.83(51)-116.42(6)°之间,相对键角范围在138.82(6)-168.59°之间。在本发明一个具体地实施例中，该聚合物的晶体学数据具体如下：
本发明提供的一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物，其结构式如下：
[Mn(C7H2N2O7)2/2(C10H8N2)]n,其中(C10H8N2)为2，2’-联吡啶，H2(C7H2N2O7)为3,5-二硝基水杨酸。发明配合物的非对称结构单元是由一个混配分子[Mn(C7H2N2O7)2/2(C10H8N2)]组成。在混配分子[Mn(C7H2N2O7)2/2(C10H8N2)]中，每个Mn(II)原子与来自2个不同3,5-二硝基水杨酸根离子的4个氧原子和来自1个2，2’-联吡啶分子的2个氮原子配位,构成了畸变的六配位MnN2O4八面体构型。通过3,5-二硝基水杨酸根离子的羟基氧和羧基氧原子把非对称结构单元桥联成沿[001]方向无限延伸的一维配位聚合链。其中Mn---N的键长为2.2245(17),和Mn---O键的键长范围在之间。相邻键角范围在55.83(51)—116.42(6)°之间,相对键角范围在138.82(6)—168.59°之间。链与链之间通过C-H…O弱氢键作用形成三维网状结构。
本发明的另一目的在于提供上述一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物的制备方法；为了实现上述的第二个目的，本发明采用了以下的技术方案：
一种制备上述3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物的制备方法：
1)称取氯化锰[MnCl2`2H2O]经溶解，加足量的碳酸钠溶液，离心分离制备成纯净的碳酸锰。再加入3,5-二硝基水杨酸[H2(C7H2N2O7)],2,2’-联吡啶[(C10H8N2)],与甲醇水[CH3OH/H2O]的混合溶剂混和搅拌1.5～3.0小时，CH3OH与H2O的体积比为1:1.5～1:3，再把所得的土黄色悬浮液封入内衬聚四氟乙烯的不锈钢反应釜中，填充度60-85％，最后将反应釜置于150～165℃的烘箱内保温一周；
2)自然冷却至室温，过滤,得到浅黄色滤液；
3)所得浅黄色滤液置于室温下自然蒸发，二个月后得到黄色晶体；
4)用蒸馏水洗涤晶体后自然干燥。
本发明的再一个目的是提供上述所述一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物在制备抗肿瘤、抗菌药物中的应用。该配位聚合物对肿瘤细胞的毒性研究结果表明，其对肿瘤细胞有选择性毒性，并且聚合物对肿瘤细胞的毒性远大于配体。
附图说明
图1为本发明化合物不对称结构单元的晶体结构图(50％probability)；
图2为本发明化合物沿[001]方向无限延伸的一维聚合链；
图3为本发明化合物沿c方向的堆积图及氢键；
图4为本发明化合物的红外光谱图；
图5为本发明化合物理论粉末衍射图。
具体实施方式
1.1试剂与仪器
所用试剂均为市售分析纯试剂，FT–IR仪(美国Nicolet公司EXUS670型)；BIUKER公司APEX CCD II型单晶衍射仪。
1.2配合物的合成
称取0.0810g(0.50mmol)氯化锰[MnCl2`2H2O]，加蒸馏水溶解，再加足量的碳酸钠溶液，离心分离并用蒸馏水洗涤5次，制成纯净的碳酸锰。然后加0.1140g(0.52mmol)3,5-二硝基水杨酸[H2(C7H2N2O7)],0.0780g(0.50mmol)2,2--联吡啶[C10H8N2`]，跟15ml甲醇/蒸馏水(V:V＝1:2)混合溶剂混合搅拌2小时，再将所得的土黄色悬浮液封入内衬聚四氟乙烯的不锈钢反应釜中，填充度70％，最后将反应釜置于150℃的烘箱内，5天(800h)后停止加热，自然冷却至室温，过滤除去固体不溶物，得到浅黄色液体，滤液在空气中自然蒸发,二个月后析出黄色块状晶体。用蒸馏水洗涤晶体后自然干燥。
1.3将合成所获得的黄色块状晶体测试并解析其晶体结构：
选取大小为0.260mm×0.220mm×0.120mm的单晶，在APEX CCD II型单晶衍射仪上收集衍射数据,采用MoKα射线()，在1.71°≤θ≤25.00°范围内以ω和扫描方式共收集到23846个数据，其中独立衍射点3129个[R(int)≥0.0410]，3129个[F0 2≥2σ(F0 2)]可观察衍射点用于结构修正，衍射强度数据经Lp因子和经验吸收校正。全部非氢原子采用直接法获得，非氢原子坐标及其各向异性温度因子采用全矩阵最小二乘法修正,碳原子上的氢原子通过理论加氢得到。主要晶体学数据列于表1。w＝1/[σ2(F0 2)+(0.0330×P)2+0.85×P],P＝(F0 2+2Fc 2)/3。最后一轮修正的S值为1.045，(Δ/σ)max为0.001，差值Fourier上的最大残余峰Δρmax＝324e/nm3,最小残余峰Δρmin＝–269e/nm3。所有计算使用SHELX–97程序[6,7]，在WIN7上进行；
表1为一种一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物,其晶体学数据如下:
其中图1为本发明化合物不对称结构单元的晶体结构图(50％probability)；图2为本发明化合物沿[001]方向无限延伸的一维聚合链；图3为本发明化合物沿c方向的堆积图及氢键；图1显示本发明配合物[Mn(C7H2N2O7)2/2(C10H8N2)]n,其中(C10H8N2)为2，2’-联吡啶，H2(C7H2N2O7)为3,5-二硝基水杨酸；且该晶体结构由一个非对称结构单元的混配分子[Mn(C7H2N2O7)2/2(C10H8N2)]组成。
在混配分子[Mn(C7H2N2O7)2/2(C10H8N2)]中，每个Mn(II)原子与4个氧原子和2个氮原子配位。4个配位氧原子来自2个不同的3,5-二硝基水杨酸根离子,2个配位氮原子来自2，2’-联吡啶分子。6个配位原子构成了畸变的六配位MnN2O4八面体构型。通过3,5-二硝基水杨酸根离子的羟基氧和羧基氧原子把非对称结构单元桥联成沿[001]方向无限延伸的一维配位聚合链。
表2列出了主要的键长键角，Mn---N的键长为2.2245(17),和Mn---O键的键长范围在之间。相邻键角范围在55.83(51)-116.42(6)°之间,相对键角范围在138.82(6)-168.59°之间；链与链之间通过C-H…O弱氢键作用形成三维网状结构。
表2
Symmetry transformations used to generate equivalent atoms:#1x,-y+3/2,z-1/2#2x,-y+3/2,z+1/2
这一晶体结构的独特之处，一是3,5-二硝基水杨酸根离子不仅发挥了很好的配位作用,而且还利用羟基氧和羧基氧原子把非对称结构单元桥联成沿[001]方向无限延伸的一维聚合链。二是3,5-二硝基水杨酸根离子中的2个硝基没有参与配位，仍然保留着硝基化合物的性质；图4和图5为该晶体结构的红外光谱图和粉末衍射图。
上述所述一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物在制备抗肿瘤、抗菌药物中的应用；该配位聚合物对肿瘤细胞的毒性研究结果表明，其对肿瘤细胞有选择性毒性，并且聚合物对肿瘤细胞的毒性远大于配体。
Claims (5)
1.一种一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物，其晶体学数据如下：
2.如权利要求1所述的一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物，其特征在于：该聚合物的晶体学数据具体为：
3.如权利要求1所述的一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物，其特征在于：Mn---N的键长为2.2245(17),和Mn---O键的键长范围在 之间，相邻键角范围在55.83(51)-116.42(6)°之间,相对键角范围在138.82(6)-168.59°之间。
4.一种制备如权利要求1所述的一种一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物的方法，其特征在于该方法包括以下的步骤：
1)称取氯化锰[MnCl2`2H2O]经溶解，加足量的碳酸钠溶液，离心分离制备成纯净的碳酸锰。再加入3,5-二硝基水杨酸[C6H2(OH)(CO2)(NO2)2],2,2-联吡啶[C10H8N2`]与甲醇水[CH3OH/H2O]的混合溶剂混和搅拌1.5～3.0小时，CH3OH与H2O的体积比为1:1.5～1:3，再把所得的土黄色悬浮液封入内衬聚四氟乙烯的不锈钢反应釜中，填充度60-85％，最后将反应釜置于150～165℃的烘箱内保温一周；
2)自然冷却至室温，过滤,得到浅黄色滤液；
3)所得浅黄色滤液置于室温下自然蒸发，二个月后得到适用于单晶测试的黄色晶体；
4)用蒸馏水洗涤晶体后自然干燥。
5.一种如权利要求1～3任意一项所述的一维链3,5-二硝基水杨酸2,2’-联吡啶锰(II)配位聚合物在制备抗肿瘤、抗菌药物上的应用。
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| CN112480174A (zh) * | 2020-11-26 | 2021-03-12 | 宁波大学 | 一种具有反铁磁作用的锰配合物及其制备方法 |
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