CN114933711B - 一种有机超分子球的制备及其在碘吸附方面的应用 - Google Patents

一种有机超分子球的制备及其在碘吸附方面的应用 Download PDF

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CN114933711B
CN114933711B CN202210625759.3A CN202210625759A CN114933711B CN 114933711 B CN114933711 B CN 114933711B CN 202210625759 A CN202210625759 A CN 202210625759A CN 114933711 B CN114933711 B CN 114933711B
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蒋志龙
吕文志
王俊
李一鸣
陈名钊
刘伟亚
吴梓浩
苗瑞
陈帮塘
王敏
王平山
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Guangzhou University
Qiannan Normal University for Nationalities
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Abstract

本发明公开了一种有机超分子球的制备及其在碘吸附方面的应用，属于新型超分子笼纳米材料合成领域。本发明通过由有机配体在金属离子的参与下配位自组装构建了一类新型金属超分子有机笼，并将其及应用于水中和空气中吸附碘。本发明分别利用六溴三亚苯为起始原料，通过在结构单元种引入三联吡啶配体单元，形成带有三亚苯结构单元的六齿三联吡啶配体，和过渡金属配位后形成内消旋四面体形状金属有机超分子笼状结构。利用其良好的碘单质吸附性质，将其应用于空气和水中含碘单质污染物的吸附应用。

Description

一种有机超分子球的制备及其在碘吸附方面的应用
技术领域
本发明涉及一种有机超分子球的制备及其在碘吸附方面的应用，属于新型超分子笼纳米材料合成领域。
背景技术
三维金属有机超分子结构在金属催化、电致发光、光催化产氢、抗癌药物、重金属离子吸附和回收利用等方面有着巨大的研究价值。因而一直是超分子化学研究的重要内容。
Jonathan Nitschke利用希弗碱和亚铁离子的四面体金属有机超分子结构可以捕获水中的白磷，形成稳定的主客体结构，将易燃的白磷稳定的保持在超分子结构内。MichitoYoshizawa利用吡啶配体和非共价芳香环单元构建的金属配位超分子笼状结构可以将荧光染料包裹在超分子空腔内，形成具有优良发光性能的金属有机超分子结构；JoostN.H.Reek，通过将水氧化催化中心通过非共价作用力富集于由吡啶和金属离子构建的三维金属超分子球中，形成了局部催化中心聚集态，使得即使在催化剂浓度极低的情况下，电催化超分子体系仍然保持较好的催化活性。刘叠等人利用多种三联吡啶有机配体在金属离子的共同作用下，形成了具有聚集态发光的四面体超分子结构，这一结构在荧光探针、重金属离子检测及发光材料等领域具有重大潜在应用价值。Li Chunju等人报道了一种能够吸附碘分子的二维有机凝胶材料可以吸附空气和水中单质碘，可以应用于核电站的放射性碘蒸汽及含放射性碘废水的处理。此外，放射性碘控制性释放应用于甲状腺疾病的治疗等领域有着重要的潜在应用价值。
目前已报道的碘吸附材料报道较少，主要有有机凝胶材料、金属配合物大环、金属有机框架材料。现有的碘吸附剂，存在料结构复杂、制备成本高、材料的吸附功能受制备过程影响较大等缺点。
发明内容
本发明利用多臂三联吡啶有机配体，并利用它和过渡金属离子的配位自组装制备了一种新型三联吡啶金属有机配位球状超分子结构，这一类球状超分子结构在光催化产氢、碘吸附、荧光探针、光电转换材料领域有良好的应用前景。本发明提供了新型三联吡啶有机配体及其超分子球的合成方法，由于三联吡啶超分子结构中大量的金属离子及阴离子存在，使得超分子结构内存在丰富的静电作用及金属离子与配体之间的电荷转移作用；同时，由于在超分子结构内引入了三亚苯基团，增加了超分子内部的Π-Π作用力，当选用适当的金属离子配位可以形成催化中心、光敏中心富集的光电转换功能超分子材料，在主客体相互作用、分子识别、发光材料领域有巨大的应用前景。
本发明提供了一种有机超分子球，所述有机超分子球的结构如下：
所述超分子球的结构通式为M12L4，其中M为过渡金属离子，包括铁、钴、镍、锌、钴、铜、镉、锰、钌、镍等；L为有机配体。所述有机超分子球，是有机配体与金属离子在溶液中配位自组装形成得到的具有三维超分子结构的有机超分子球。
有机配体L结构如下式(I)。其中R为碳链、聚醚链、聚醚砜链、聚芳香烃环链或者多肽链，以及其他具有催化、发光、生物活性等官能作用的原子及原子团。其中以原子个数计算(包括碳原子及氧、硫、氮等其他杂原子)总数不超过50个；n的取值范围是0-3。
有机配体L可以通过在三亚苯为基元，延长延长芳香环从1-3个，所延长芳香环种类包含苯环、吡啶环、嘧啶环、咪唑环、吡嗪环等五元及六元芳香环。
在一种实施方式中，所述有机配体L为多臂三联吡啶有机配体。
在一种实施方式中，，所述多臂三联吡啶有机配体L的结构式如式(II)所示。
所述有机超分子球的制备：在有机溶剂氯仿和甲醇溶液中加入金属离子，通过常温搅拌或者加热回流的作用下，金属离子和有机配体相结合；随后，将溶液冷却到室温，通过离子交换的方式，使得溶液中少量的金属离子一起引入的阴离子被交换掉；溶液中的超分子析出后将目标有机超分子球从溶液中分离出来。
在一种实施方式中，具体是：在有机溶剂氯仿和甲醇溶液中加入计量比金属离子，通过常温搅拌或者加热回流的作用下，金属离子和有机配体通过金属离子配位自组装，获得结构单一、稳定的三维超分子结构；随后，将溶液冷却到室温，通过加入过量的六氟磷酸铵和双三氟甲烷磺酸锂盐通过离子交换的方式，使得溶液中少量的金属离子一起引入的阴离子被交换掉，溶液中的超分子析出后，直接通过抽滤或者离心的方法将目标超分子结构从溶液中分离出来。该方法制备过程简单、几乎定量收率。
优选方案：利用氯仿和甲醇2:1的比例将配体溶解。随后在加热条件下在混合溶液中滴加统计量的金属离子继续搅拌8小时，直待蓝色荧光消失，溶液变成无色或者淡黄色。
优选方案：六磷酸盐、四氟硼酸盐、双三氟甲烷磺酸盐被应用于将三维超分子结构从溶液中沉淀下来，在含氟阴离子的作用下，氟离子和配体中配体中氢原子形成氢键、有利于提高三维超分子结构的稳定性。
在一种实施方式中，有机超分子球的制备反应过程如下：
关于有机配体：
所述有机配体的结构式如式(I)所示；所述有机配体能够与金属离子在溶液中配位自组装，形成三维超分子结构。其中R为碳链、聚醚链、聚醚砜链、聚芳香烃环链或者多肽链，以及其他具有催化、发光、生物活性等官能作用的原子及原子团。其中R基团以原子个数计算(包括碳原子及氧、硫、氮等其他杂原子)总数不超过50个。
关于有机配体的制备：
在一种实施方式中，所述有机配体的制备方法：以六溴三亚苯作为反应起始物，通过Suzuki偶联反应，一步得到目标有机配体结构。
在一种实施方式中，所述有机配体的制备方法具体是：起始原料三亚苯在以硝基苯为溶剂，三氯化铁作为催化剂，在120℃溴代，得到六取代多溴化物；多溴化物在水/甲苯/叔丁醇混合溶剂系统重，加入钯催化剂及硼酸基三联吡啶，得到目标有机配体结构。
在一种实施方式中，所述有机配体的合成路线如下：
在一种实施方式中，有机配体的合成：三亚苯在铁催化下形成六溴三亚苯；三亚苯的2,3被溴取代，形成多溴化物；随后在氮气保护作用下，以0价金属钯配体和R取代的间位硼酸三联吡啶的作用下，形成伞型有机配体。
在一种实施方式中，有机配体的合成包括：利用甲苯和水的体系，利用二三苯基膦二氯化钯作为催化剂，以碳酸钠为碱，在氮气保护下回流72小时，随后通过柱层析或者重结晶的方法得到有机配体L1。
本发明还提供了所述有机超分子球的应用。
在一种实施方式中，所述应用是用于碘吸附；所述碘可以是空气中碘单质或者碘水溶液。
在一种实施方式中，所述应用是用于包裹客体分子；所述客体分子可以是多肽、C60、药物分子等。
本发明有益的技术效果在于：
本发明所述三维金属有机超分子结构属于金属离子-有机配体协同构建的产物，具有潜在的光电转化功能，可以包裹包括多肽、C60等客体分子、在主客体识别、药物载体、催化功能反应器等领域具有巨大的应用潜力。
和目前已经报道的金属有机笼状超分子结构相比，本发明所述的三维超分子由有机配体和过渡金属离子通过在溶液中配位形成、过程简单，方便易得。同时在超分子结构内引入了三亚苯单元，这一大共轭芳香烃结构单元有利于形成分子内和分子间Π-Π作用，在和客体作用的过程中超分子球内部存在氢键作用力和Π-Π作用，同时在超分子结构内存在多种过渡金属和有机配体的配位单元，形成多种类型非共价作用协同作用的金属有机超分子体系；具有成为光电功能材料及主客体研究的结构载体。
本发明所述三维金属有机超分子结构制备条件简单，组装条件温和，工艺可控性能强、有利于大规模生产。
本发明的三维金属有机超分子球可以用做吸附剂，比如碘吸附剂。和现有报道的碘吸附剂相比，本发明的超分子球纳米结构具有以下的优点：(1)超分子结构由有机配体和金属离子配位自组装形成，材料合成过程简单，吸附效率高(0.8g/g)，效果稳定，工艺重现性强，不受材料制备工艺的影响，吸附水中碘分子的速度快(30分钟完全吸收完全)；(2)超分子球中金属离子通过EDTA螯合后，可以将配体及碘回收，可以提高材料的重复利用，降低使用成本；(3)超分子结构由有机配体和金属螯合后形成离子型化合物，结构稳定、亲水性强，对水中的微量碘吸附具有更好的吸收效率。同时，材料本身所具备超分子笼结构，不仅在碘离子吸附应用方面，在重金属离子的吸附、限域催化、电致发光材料等领域均有潜在应用前景。
附图说明
图1为实施例1配体L的HNMR图；
图2为实施例1配体L的COSY图；
图3为实施例1配体L的二维NOE氢氢相关图；
图4为实施例1配体L的碳谱C NMR图；
图5为实施例1金属有机超分子球的氢谱图；
图6为实施例1金属有机超分子球的H-H相关图COSY图；
图7为实施例1金属有机超分子球的二维氢氢相关图NOESY图；
图8为实施例1金属有机超分子球二维NOESY图；
图9为[Zn12L4]的2D DOSY spectrum(500MHz)；
图10为配体L的MOLDI-TOF-MS质谱图；
图11为金属有机纳米球Zn12L4的质谱图(A)ESI-MS spectrum and(B)TWIM-MSplots of[Zn12L4](PF6 -as counterion)；
图12为金属有机纳米球Zn12L4的质谱同位素分布图；
图13为金属有机纳米球Zn12L4的晶体外观图；
图14为金属有机纳米球Zn12L4的晶体结构示意图；
图15为金属有机纳米球Zn12L4的晶体堆积图；
图16为有机超分子球Zn12L4应用于吸附空气中碘单质；
图17为有机超分子球Zn12L4应用于吸附水中碘单质；
图18为有机超分子球Zn12L4与C6o形成主客体结构所示的质谱信息图。
具体实施方式
实施例1
中间体6-溴三亚苯的合成
将1.00g(4.38mmol)三亚苯溶于50mL硝基苯中，加入100mg铁粉，3.15g(39.42mmol)液溴缓慢的加入到上述混合溶液中，随后反应溶液缓慢升温至205℃，反应3小时，随后将反应液冷却至室温，反应液中加入50毫升乙醚，抽滤形成的固体，固体反复用水、乙酸乙酯、乙醚、二氯甲烷洗涤，最后得到淡黄色固体粉末2.80g，收率91.2％，直接投于下一步反应。
有机配体L的合成：
六溴三亚苯(200.2mg,285.6μmol)和三硼酸苯基三联吡啶(786.3mg,2.23mmol)置于250mL单口瓶中，水/叔丁醇/甲苯(200mL,V:V:V,3:1:3)和碳酸钠(544.9mg,5.14mmol)加入到上述溶液中，反应混合物脱气3分钟后，加入Pd(PPh3)2Cl2(72.07mg,102.8μmol)，反应混合物在氮气保护下回流3天，随后冷却至室温，氧化铝柱层析得到白色固体粉末447.0mg，收率为62％。1H NMR(500MHz,CDCl3)δ8.90(s,6H,Ph-Ha),δ8.59-8.58(d,12H,tpy-H6,6'),δ8.53-8.51(m,24H,tpy-H3',5',tpy-H3,3”),δ7.93(s,6H,Ph-Hb),δ7.80-7.76(m,18H,tpy-H4,4”,Ph-Hc),δ7.53-7.51(d,6H,J＝10Hz,Ph-He),δ7.48-7.55(m,6H,Ph-Hd),δ7.24-7.22(t,12H,tpy-H5,5”).13C NMR(101MHz,CDCl3)δ156.14,155.77,150.14,149.02,141.92,139.57,138.40,136.59,131.01,129.21,129.01,128.79,126.03,125.65,123.60,121.21,119.08.MALDI-TOF(m/z):calcd.for[M+H+]+2072.77,found 2072.56.
图1～图4依次为实施例1配体L的HNMR图、COSY图、NOESY图、C NMR图。相关图谱能够证明相关配体的纯度，是获得目标结构的有力证据。
金属有机超分子球的合成[Zn12L4].
有机配体L(23.0mg,11.1μmol)溶于氯仿和甲醇(20mL,3：1/v/v)混合溶液中,Zn(NO3)2·6H2O(10.4mg,34.9μmol)溶于10毫升甲醇中缓慢加入到上述混合溶液中，滴加完毕后将混合溶液升温至65℃，加热回流8小时后冷却至室温，随后加入1g六氟磷酸铵溶液中，大量的白色沉淀从溶液中析出，抽滤。滤饼用水和甲醇依次洗涤，得到白色固体粉末33.8mg，收率为97％。1H NMR(500MHz,DMF/CD3CN)δ9.33(s,24H,B-tpy-H3',5'),δ9.25(s,12H,B-Ph-Ha),δ9.14(s,12H,B-Ph-Hb),δ8.81(s,12H,A-Ph-Ha),δ8.62-8.60(m,36H,B-tpy-H3,3”,B-Ph-He),δ8.24-8.22(m,24H,A-Ph-Hc,A-Ph-He),δ8.19-8.16(d,24H,J＝15Hz,A-tpy-H3,3”),δ8.07(s,24H,A-tpy-H3',5”),δ7.99-7.97(m,12H,A-Ph-Hd),δ7.81-7.77(m,24H,B-tpy-H4,4”),δ7.75-7.71(m,24H,A-tpy-H4,4”),δ7.65-7.62(m,24H,A-Ph-Hb,B-Ph-Hd),δ7.60-7.59(d,24H,J＝5Hz,A-tpy-H6,6”),δ7.49-7.48(d,24H,J＝5Hz,B-tpy-H6,6”),δ7.42-7.40(d,12H,J＝10Hz,B-Ph-Hc),δ7.14-7.12(m,24H,A-tpy-H5,5”),δ7.02-6.99(m,24H,B-tpy-H5,5”).ESI-MS(12553.42calcd.for C576H360F144N72P24Zn12with PF6-):m/z 2364.90(M-5PF6-)5+(calcd m/z:2365.70),1946.76(M-6PF6-)6+(calcdm/z:1947.26),1648.09(M-7PF6-)7+(calcd m/z:1648.37),1424.11(M-8PF6-)8+(calcdm/z:1424.20),1249.31(M-9PF6-)9+(calcd m/z:1249.85),1110.11(M-10PF6-)10+(calcdm/z:1110.38),996.00(M-11PF6-)11+(calcd m/z:996.25)。
表1金属超分子球的单晶衍射数据：[Zn12L4].
aR1＝Σ||Fo|–|Fc||/Σ|Fo|；wR2＝[Σ[w(Fo 2–Fc 2)2]/Σ[w(Fo 2)2]]1/2
实施例2有机超分子球应用于吸附空气中碘单质
将实施例1制备的1g金属超分子固体置于样品瓶中，加入碘0.5g，随后盖紧瓶盖，待碘自然挥发，12小时候可以观察到碘单质消失，称取金属有机超分子的质量，约为1.5g。
吸附效果如图16所示。
实施例3有机超分子球应用于吸附水中碘单质
将0.1g碘溶于10毫升水中，将实施例1制备的金属有机超分子0.3g固体粉末加入到上述碘和水的溶液中。结果显示，静止1小时，金属超分子结构变为深棕色，而水溶液变成无色，说明碘单质在水溶液中全部被金属有机纳米金属球吸收。吸附效果如图17所示。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (7)

1.一种有机超分子球，其特征在于，所述超分子球的结构通式为M12L4，其中M为过渡金属离子，选自铁离子、钴离子、镍离子、锌离子、铜离子、镉离子、锰离子、钌离子中的任意一种；L为有机配体，所述超分子球的结构如下：
其中，有机配体L结构式(I)；其中R为碳链或氢，R基团以原子个数计算，总数不超过50个；
2.根据权利要求1所述的有机超分子球，其特征在于，所述有机配体的制备方法具体是：起始原料三亚苯在以硝基苯为溶剂，三氯化铁作为催化剂，溴代得到六取代多溴化物；多溴化物在水/甲苯/叔丁醇混合溶剂系统中，加入钯催化剂及硼酸基三联吡啶，得到目标有机配体结构。
3.权利要求1所述的有机超分子球的制备方法，其特征在于，所述制备方法是：在有机溶剂氯仿和甲醇溶液中加入金属离子，通过常温搅拌或者加热回流的作用下，金属离子和有机配体相结合；随后，将溶液冷却到室温，通过离子交换的方式，使得溶液中少量的金属离子与一起引入的阴离子被交换掉；溶液中的超分子析出后将目标有机超分子球从溶液中分离出来。
4.权利要求1所述的有机超分子球的制备方法，其特征在于，有机超分子球的制备反应过程如下：
5.权利要求1-2任一所述的有机超分子球的应用。
6.根据权利要求5所述的应用，所述应用是用作吸附剂或者包裹客体分子。
7.根据权利要求5所述的应用，所述应用是用于光催化产氢、荧光探针或者光电转换材料领域。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN109603764A (zh) * 2019-01-24 2019-04-12 浙江师范大学 一种有机功能材料及其制备方法和在碘吸附中的应用
CN113214494A (zh) * 2021-05-21 2021-08-06 吉林大学 一种螺旋超分子材料及其制备方法与应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107417913A (zh) * 2017-08-22 2017-12-01 广东工业大学 一种纳米有机微孔聚合物和吸附饮用水中重金属的方法
CN109603764A (zh) * 2019-01-24 2019-04-12 浙江师范大学 一种有机功能材料及其制备方法和在碘吸附中的应用
CN113214494A (zh) * 2021-05-21 2021-08-06 吉林大学 一种螺旋超分子材料及其制备方法与应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Mingzhao Chen等.Highly Stable Spherical Metallo-Capsule from a Branched Hexapodal Terpyridine and Its Self-Assembled Berry-type Nanostructure.《J. Am. Chem. Soc.》.2018,第140卷第2555页左栏第1段、第2556页右栏步骤1、第2558页右栏倒数第2段、第2559页步骤2、第2560右栏第2段、第S5页第3部分、第S6页第2段. *
Vandana Bhalla等.Triphenylene derivatives: chemosensors for sensitive detection of nitroaromatic explosives.《Dalton Trans.》.2012,第42卷第970页左栏步骤1. *

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