CN111875642B - 一种多三联吡啶金属有机配体化合物及其组装的五元花环状超分子和制备 - Google Patents
一种多三联吡啶金属有机配体化合物及其组装的五元花环状超分子和制备 Download PDFInfo
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- CN111875642B CN111875642B CN202010803893.9A CN202010803893A CN111875642B CN 111875642 B CN111875642 B CN 111875642B CN 202010803893 A CN202010803893 A CN 202010803893A CN 111875642 B CN111875642 B CN 111875642B
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一种基于三联吡啶金属配位的五元花环状超分子合成方法。该超分子由一种含有多个三联吡啶及金属钌的配体与过渡金属离子在溶剂中自驱动形成巨型五元花环状超分子。配体与过渡金属可精确的反应生成单一五聚产物,无其他副产物产生。配体及最终组装产物通过核磁、质谱、扫描电镜等测试进行了结构表征以及分子量的确定。该超分子具有较大的分子量和良好的溶解性能,分子结构具有对称性和美学性能,且能够实现凝胶化。
Description
技术领域
本发明涉及一种五元花环状超分子的合成方法,特别涉及一种多三联吡啶金属有机配体化合物及由该配体与金属离子通过自装置形成的五元花环状超分子及其制备方法,属于新型超分子合成领域。
背景技术
在超分子化学中,金属-配体配位作用在超分子的构建中起着重要的作用。配体与金属离子之间的配位驱动自组装可以产生复杂的二维、三维和无限的金属有机超分子结构,其复杂性和功能性可以得到增强。在过去的三十年中,配位驱动的自组装的金属有机超分子得到大量的报道,含氮有机配体占据了这一领域的大部分超分子组装,从单齿,双齿到三齿配体。利用单齿吡啶基配体和双齿类联吡啶配体的自组装构建超分子结构在过去几十年中取得了卓有成效的发展,无论是在其广泛的结构还是功能上的应用。此外,在三齿三联吡啶自组装化学领域,化学工作者们一直在寻求同时具有数学和艺术美学的复杂和功能结构的合成。必须说,精确控制超分子结构的形状和大小在今天仍然被视为一个巨大的挑战,因为有机配体的灵活性和相差不大的热力学或动力学稳定性可能导致混合的产物。随着超分子催化、纳米材料应用、生命科学应用和储能等方面的研究的不断深入,结构的可控制对于实现其潜在功能和应用具有重要意义。
寻求及发展具有特殊形貌的化学结构是化学工作者的重要任务之一,这一方面增加化学的艺术性,另一方面根据结构决定性质从而决定应用,具有特殊形貌的化学结构因此具有很重要的潜在研究价值。在金属有机配位化学中,通过分步合成更复杂的金属有机配体,预期就能够获得更为复杂的金属超分子。
精确控制金属大环向离散结构的自组装仍然是超分子化学领域的目标和挑战之一。有效地控制组装五元花环是个巨大的挑战。制备花环形状的超分子结构,配体组件往往需要包含内外两层的特征,内层形成中心的花柄,而外层对应花瓣的结构。根据角度原则,制备五元的配体角度应该是108度左右。但是在化学结构式中具有108度角的结构很少,此外,一般的配体都具有柔韧性因而使得角度可调,所以配体在构筑超分子时,其方向的保守性并不是很严格。
现有技术中,还没有具有五元对称花状超分子的报道。
发明内容
为了获得具有五元花状结构的超分子,本发明第一目的在于,提供一种特殊结构的多三联吡啶金属有机配体化合物。
本发明第二目的在于,提供了一种所述的多三联吡啶金属有机配体化合物的制备方法。
本发明第三目的在于,提供一种具有特殊五元花状对称结构的五元花环状金属有机超分子。
本发明第四目的在于,提供一种所述的特殊五元花状对称结构的五元花环状金属有机超分子的制备方法。
本发明目的在于构建五元花状结构的超分子,为了实现上述技术目的,本发明首先提供了一种多三联吡啶金属有机配体化合物,其具有式1结构:
其中,Ru金属钌。
研究发现,得益于所述的式1配体基团以及结构片段的特性,有助于组装得到具有五元对称花状结构的超分子。
本发明第二目的在于,提供一种所述的多三联吡啶金属有机配体化合物的制备方法,由式2化合物和式3化合物进行偶联反应得到:
本发明中,所述的偶联反应可基于现有手段实现,优选地,可采用铃木反应催化剂催化偶联得到。优选地,所述的催化剂为四三苯基膦钯。反应过程的催化剂的用量为催化量。反应体系中,还允许添加缚酸剂,例如氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的至少一种。
优选地,反应的溶剂为能实现式2和式3原料溶解为宜,优选为乙腈、三氯甲烷、甲醇、四氢呋喃中的至少一种。优选地,反应温度为回流。
本发明中,所述的式2化合物由式4化合物和式5化合物配位反应得到;
式4化合物和式5化合物配位反应过程的溶剂例如为三氯甲烷与甲醇的混合溶剂。反应过程中添加缚酸剂作为催化剂,所述的缚酸剂例如为氮乙基吗啉。反应过程中的温度为回流。反应时间可基于反应监控结果进行调整。
式4化合物由式6化合物和RuCl3经反应得到。
本发明中,式6和RuCl3配位的反应溶剂为乙醇、甲醇、氯仿等可溶解式6的溶剂。反应过程的温度例如为60~100℃,优选为回流温度。
优选地,所述的式5化合物由式7的2,7-硼酸酯和式8化合物偶联得到;
所述的R为C1~C6的烷烃基,或者相邻的R之间环合形成包含B和O在内的五元或者六元环基。
本发明所述的制备方法,采用所述的式7和式8进行偶联反应,可以意外地成功合成实施例的式5中间体。
本发明中,式5合成过程的条件可以参考常规的铃木偶联条件,例如,在缚酸剂和四三苯基膦钯催化下进行。
本发明所述的多三联吡啶金属有机配体化合物的制备方法,整体合成线路见反应式1:
反应式1
本发明中,所述的式6化合物以及其他的中间体,均可采用现有方法进行合成制备。
作为优选,所述的多三联吡啶金属有机配体化合物的制备方法,包括以下步骤:
(1)2,7-双(2,2’:6’,2”-三联吡啶基)萘S3的制备:
将2,7-二溴萘、联硼酸频哪醇酯、醋酸钾、催化剂[1,1’-双(二苯基膦)二茂铁]二氯化钯反应制得S2产物;将S2产物和4'-溴-2,2':6',2”-三联吡啶、缚酸剂、催化剂四三苯基膦钯反应,制得S3产物:
(2)有机化合物S6的制备:
将3,5-二甲酰基溴苯,2-乙酰基吡啶和氢氧化钠在乙醇溶液中常温搅拌,然后直接加入25~28%的氨水,升温搅拌回流,停止反应,制得S5。将S5、2,6-二甲氧基苯硼酸、氢氧化钠、四三苯基膦钯作为催化剂,在氮气保护的条件下加热回流反应,制得S6。
(3)金属有机化合物S8的制备:
将S6、液溴回流反应制得S7,将S7和RuCl3在60~100℃下进行配位反应,获得S8;
(4)多三联吡啶金属有机配体的制备:
将S8和S3在缚酸剂下进行配位反应,制得S9;将S9和4'-苯硼酸-2,2':6',2”-三联吡啶、碳酸钾、催化剂四三苯基膦钯下反应,制得所述的多三联吡啶金属有机配体;
进一步优选的制备方法:包括以下步骤:
(1)2,7-双(2,2’:6’,2”-三联吡啶基)萘S3的制备:
将2,7-二溴萘、4eq的联硼酸频哪醇酯与醋酸钾加入圆底烧瓶,四氢呋喃作为溶剂,0.12eq的催化剂[1,1’-双(二苯基膦)二茂铁]二氯化钯加入圆底烧瓶,进行氮气保护,在85℃搅拌回流条件下反应24小时。反应结束后冷却至室温,以水和二氯甲烷萃取,收集有机相减压蒸馏除去溶剂。加入微量甲醇和大量石油醚重结晶,减压过滤收集液体,减压蒸馏除去溶剂后加入微量甲醇后加入大量水,减压过滤收集固体,烘干得到白色固体S2。将化合物2,7-二硼酸酯基萘、3eq的4'-溴-2,2':6',2”-三联吡啶、6eq的氢氧化钠加入圆底烧瓶,加入四氢呋喃作为溶剂,加入0.12eq的催化剂四三苯基膦钯,对装置进行氮气保护,85℃下搅拌回流反应48小时。反应结束后,冷却至室温,旋蒸除去溶剂,加入二氯甲烷与铝粉拌样装柱,以二氯甲烷和石油醚混合作为淋洗剂。旋蒸后得到白色粉末状固体S3。
(2)有机化合物S6的制备:
将3,5-二甲酰基溴苯,2eq的2-乙酰基吡啶和4eq的氢氧化钠一起加入到圆底烧瓶中,在乙醇溶液中常温搅拌10小时,然后直接加入25~28%的氨水200mL(过量),升温搅拌回流20小时,停止反应,冷却至室温后减压抽滤得到淡黄色粗产物,将粗产物用异丙醇超声回流2-3次,冷却至常温后抽滤收集固体,干燥得到纯白色固体S5。将S5、1eq的2,6-二甲氧基苯硼酸、3eq的氢氧化钠加入烧瓶,加入四氢呋喃和少量水作为溶剂,加入0.06eq的四三苯基膦钯作为催化剂,在氮气保护的条件下加热回流反应10小时。反应结束后,冷却至室温,减压蒸馏除去溶剂,加入二氯甲烷与铝粉拌样装柱,以二氯甲烷和石油醚混合作为淋洗剂。减压蒸馏后得到白色粉末状固体S6。
(3)金属有机化合物S8的制备:
将上一步得到的S6溶于少量的三氯甲烷溶剂中,液溴溶解在三氯甲烷中加入恒压滴液漏斗,缓慢滴加,加热回流反应24小时。反应结束后冷却至室温,加入过量碳酸氢钠水溶液和亚硫酸氢钠水溶液调节至体系呈中性,使用二氯甲烷萃取,收集有机相并减压蒸馏得到白色粉末状固体S7。
将S7溶解在三氯甲烷与甲醇的混合溶剂中,再加入2,4eq的RuCl3·3H2O,在80℃下反应24小时,待冷却至室温后,加压过滤收集固体,用甲醇洗涤数次,在真空干燥箱中烘干得到棕色固体产物S8。
(4)多三联吡啶金属有机配体的制备:
将S8与2eq的S3加入三氯甲烷与甲醇的混合溶剂中,滴加数滴氮乙基吗啉作为催化剂,加热回流反应48小时。反应结束后,冷却至室温,减压蒸馏除去溶剂,加入二氯甲烷与铝粉拌样装柱,以二氯甲烷和甲醇混合作为淋洗剂。减压蒸馏后得到红色粉末状固体S9。
将S9与12eq的4'-苯硼酸-2,2':6',2”-三联吡啶、16eq的碳酸钾加入圆底烧瓶,加入乙腈、三氯甲烷、甲醇作为混合溶剂,超声至固体完全溶解,加入0.2eq的催化剂四三苯基膦钯,在氮气保护下加热搅拌回流反应48小时。反应结束后,减压蒸馏除去溶剂,加入二氯甲烷和铝粉拌样装柱,以二氯甲烷和甲醇为淋洗剂,减压蒸馏除去溶剂得到红色固体即为目的多三联吡啶金属有机配体。
本发明还提供了一种五元花环状金属有机超分子,其具有式A结构:
其中,
Ru为金属钌;M为Fe和/或Zn。
本发明所述的超分子,具有对称的五元花状结构。
本发明还提供了一种所述的五元花环状金属有机超分子的制备方法,将式1的多三联吡啶金属有机配体化合物和M离子源在180±5℃下进行配位反应得到;
多三联吡啶金属有机配体化合物和M离子源的摩尔比为1:2。
本发明中,如何构建对称的五元花状结构的材料,并改善五元花状结构的选择性,避免杂相的形成是本发明制备方法主要面临的技术问题。为解决该技术问题,本发明研究发现,创新地采用所述的式1配体有助于形成所述的五元花状结构,但研究发现,仅仅采用式1配体还不足以成功构建所述的花状结构,还必须基于M离子源、M离子源的摩尔比和配位温度等条件的联合控制。研究发现,在所述的配体的基础上,进一步配合所述的M离子种类、用量和配位温度的协同作用下,能够意外地制得具有五元花状结构的超分子,不仅如此,还能够避免杂相的形成。
本发明中,采用所述的式1的配体和所述的Fe(II)和Zn(II)的联合控制,进一步配合所述的比例和温度的协同控制,能够意外地构建所述的五元花状超分子,不仅如此,还能够降低杂相。
本发明中,所述的M离子源为可溶性的亚铁源和/或锌源。本发明中,所述的亚铁源和/或锌源可和所述的式1配体协同,能够意外地利于构建得到所述的五元对称花状结构的超分子。
本发明中,所述的亚铁源为Fe2+的水溶性盐,优选为氯化亚铁、硝酸亚铁、醋酸亚铁、硫酸亚铁中的至少一种。所述的锌源为Zn2+的水溶性盐,优选为氯化锌、硝酸锌、醋酸锌、硫酸锌中的至少一种。本发明中,所述的亚铁源、锌源可以带有结晶水或者不带结晶水,优选带有结晶水。
本发明中,所述的配位溶剂为可溶解各原料的溶剂,优选地,配位反应的溶剂为乙二醇和乙腈的混合溶剂。二者的混合比例没有特别要求,可在反应温度下,是原料处于溶解状态下即可。
本发明中,配位反应的时间不低于8h;优选为10~12h。
进一步优选的五元花环状金属有机超分子的制备,
将式1的多三联吡啶金属有机配体溶解在乙腈中,用乙二醇溶解金属离子FeCl2·4H2O,将溶液混合后加热回流,进行配位组装,回收得到所述的超分子。优选的,所述的回收方法例如为:向配位反应体系中加入过量的双三氟甲磺酸亚胺锂盐的饱和甲醇溶液进行沉淀,固液分离后洗涤即得。
本发明还提供了一种所述的五元花环状金属有机超分子的应用,用作凝胶材料。
本发明所述的超分子凝胶的制备方法,将组装后的产物(超分子)溶解后,放置一段时间,即可凝胶化。
例如,将所述的超分子溶解于良性溶剂(例如乙腈或DMF)中,精制3-5天,即可凝胶化。溶解后的超分子溶液的浓度优选不低于0.1mmol/ml。
有益效果
1、本发明提供了一种全新结构的多三联吡啶金属有机配体化合物。
2、本发明提供了一种具有五元对称花状结构的金属有机超分子。
3、本发明研究发现,基于所述的式1配体和所述的特殊的金属在所述的特殊的条件下的组装特性,可以意外地获得所述的五元对称花状结构的金属有机超分子,并且能够意外地降低杂相。
附图说明
【图1】为实施例1制备的S2的H1NMR谱图;
【图2】为实施例1制备的S3的H1NMR谱图;
【图3】为实施例1制备的S5的H1NMR谱图;
【图4】为实施例1制备的S6的H1NMR谱图;
【图5】为实施例1制备的S7的H1NMR谱图;
【图6】为实施例1制备的S9的H1NMR谱图;
【图7】为实施例1制备多三联吡啶金属有机配体的H1NMR谱图;
【图8】为实施例1制备的五元花环状金属有机超分子的H1NMR谱图;
【图9】为实施例2制备的五元花环状金属有机超分子的ESI-MS谱图;
【图10】为实施例3制备的五元花环状金属有机超分子的TEM谱图。
【图11】为实施例2制得的凝胶的图片;
【图12】为实施例2制得的凝胶的SEM图;
具体实施方式
以下实施例旨在进一步说明本发明内容,而不是限制本发明权利要求的保护范围。
实施例1:
2,7-二硼酸酯基萘(S2):
将2,7-二溴萘(500.0mg,1.75mmol),联硼酸频哪醇酯(1.1g,4.2mmol),醋酸钾(1.4g,14.26mmol),催化剂[1,1’-双(二苯基膦)二茂铁]二氯化钯(154.0mg,0.21mmol),THF(15ml)加入50mL圆底烧瓶,进行氮气保护,在85℃下加热搅拌24小时。反应结束后冷却至室温,以水和二氯甲烷萃取,收集有机相减压蒸馏除去溶剂。加入微量甲醇和大量石油醚重结晶,减压过滤收集液体,旋蒸除去溶剂后加入微量甲醇后加入大量水,减压过滤收集固体,干燥后得到产物565.0mg,收率为85%。核磁1H图为图1所示,核磁数据为:1HNMR(400MHz,CDCl3)δ8.34(s,2H,Hc),7.80-7.78(d,2H,J=4Hz,Ha),7.74-7.72(d,2H,J=4Hz,Hb),1.31(s,24H,H-CH3).13C NMR(101MHz,CDCl3)δ137.16,132.44,131.54,126.77,84.63,83.87,77.34,77.01,76.71,24.93.
2,7-双(2,2’:6’,2”-三联吡啶基)萘S3:
将2,7-二硼酸酯基萘(500.0mg,0.95mmol)与4'-溴-三联吡啶(705.0mg,2.20mmol),氢氧化钠(300.0mg,7.40mmol),150mL四氢呋喃作为溶剂,催化剂四三苯基膦钯(216.0mg,0.20mmol)加入250mL圆底烧瓶,在氮气保护下85℃搅拌加热反应48小时。反应结束后,冷却至室温,减压蒸馏除去溶剂,拌样装柱,以二氯甲烷和石油醚混合作为淋洗剂。减压蒸馏后得到白色粉末状固体,得到产物364.0mg,收率65%。核磁1H图为图2所示,核磁数据为:1H NMR(400MHz,CDCl3)δ8.94(s,4H,tpy-H3’5’),8.79-8.78(d,8H,J=2Hz,tpy-H33”),8.73-8.71(d,8H,J=4Hz,tpy-H66”),8.56(s,2H,Ph-Ha),8.12-8.10(d,2H,J=8Hz,PH-Hb),8.06-8.04(d,2H,J=8Hz,Ph-Hc),7.92-7.89(t,4H,tpy-H44”),7.39-7.36((t,4H,tpy-H55”).
3,5-双(2,2’:6’,2”-三联吡啶基)溴苯S5:
3,5-二甲酰基溴苯(3.54g,2mmol)、2-乙酰基吡啶(5.14g,4.8mmol)、NaOH(0.8g,24mmol)溶解于200ml乙醇中,室温下搅拌12小时,加入氨水(28%,150mL)后加热回流搅拌反应48小时,冷却后减压过滤,收集固体后使用甲醇加热回流,再次减压过滤收集固体,干燥后得到白色固体粉末9.97g,收率为85.0%.核磁1H图为图3所示,核磁数据为:1H NMR(400MHz,CDCl3)δ8.78(s,4H,tpy-H3',5'),8.75-8.74(d,J=4Hz,4H,tpy-H 6,6”),8.71-8.69(d,J=8Hz,4H,tpy-H3,3”),8.29(s,1H,Ph-Ha),8.12(s,2H,Ph-Hb),7.92-7.88(t,J=16Hz,4H,tpy-H4,4”),7.39-7.36(t,J=12Hz,4H,tpy-H5,5”).13C NMR(101MHz,CDCl3)δ156.21,155.99,149.18,148.75,141.50,136.96,130.78,125.13,124.01,121.47,119.10,77.33,77.22,77.01,76.70.
有机化合物S6:
3,5-双(2,2’:6’,2”-三联吡啶基)溴苯S5(2g,3.42mmol)、1,3-二甲氧基苯硼酸(0.78g,3.6mmol)、NaOH(0.41g,10.3mmol)溶解于300ml THF中,加入催化剂四三苯基膦钯Pd(PPh3)4(0.462g,0.4mmol),在氮气保护下加热回流搅拌反应12小时。反应结束后冷却至室温,拌样装柱,使用二氯甲烷和石油醚作为淋洗剂,减压蒸馏除去溶剂后得到白色固体粉末1.50g,收率为65%。核磁1H图为图4所示,核磁数据为:1H NMR(500MHz,CDCl3)δ8.87(s,4H,tpy-H3',5'),8.75-8.74(d,J=4Hz,4H,tpy-H6,6”),8.72-8.70(d,J=8Hz,4H,tpy-H3,3”),8.38(s,1H,Hd),7.98(s,2H,Hc),7.92-7.89(t,J=12Hz,4H,tpy-H4,4”),7.38-7.35(m,5H,tpy-H5,5”,Ph-Ha)6.73-6.72(d,J=4Hz,2H,Hb),3.79(s,6H,H-OCH3).13C NMR(101MHz,CDCl3)δ161.86,158.19,157.70,156.34,155.68,150.45,150.29,149.10,139.41,138.90,136.90,131.04,130.85,124.66,123.76,121.45,119.49,118.61,118.47,105.22,104.14,55.93.
有机化合物S7:
有机化合物S6(500mg,0.74mmol)溶解于50ml氯仿中,液溴(5mL,97.5mmol)溶解在5ml氯仿中逐滴加入反应体系中,加热回流搅拌反应24小时后冷却至室温,加入饱和亚硫酸氢钠水溶液和饱和碳酸氢钠水溶液调节溶液至中性。使用二氯甲烷进行萃取并收集有机相,减压蒸馏除去溶剂后收集固体,使用甲醇洗涤1-2次后得到白色固体粉末494mg,收率为80%.核磁1H图为图5所示,核磁数据为:1H NMR(500MHz,CDCl3)δ8.87(s,4H,tpy-H3',5'),8.76-8.75(d,J=4Hz,4H,tpy-H6,6”),8.73-8.71(d,J=8Hz,4H,tpy-H3,3”),8.49(s,1H,Hd),8.12(s,2H,Hc),7.94-7.91(t,J=12Hz,4H,tpy-H4,4”),7.86(s,1H,Ha),7.41-7.38(d,J=12Hz,4H,tpy-H5,5”),3.51(s,6H,H-OCH3).13C NMR(101MHz,CDCl3)δ156.12,155.06,149.75,149.11,139.72,137.01,135.53,134.44,131.48,129.75,125.94,123.95,121.52,119.31,113.31,60.85.
有机化合物S8:
金属有机化合物S7(200mg,0.24mmol)、RuCl3·3H2O(134.75mg,0.53mmol)溶解于50ml乙醇中,加热回流反应48小时。冷却后减压过滤收集固体,用甲醇和氯仿混合洗涤1-2次后得到红棕色固体275mg,收率为90%。因产物溶解性极差,无法用核磁表征。
金属有机化合物S9:
将S8(80.0mg,0.06mmol)与S3(85.0mg,0.12mmol)加入250mL圆底烧瓶,加入50mL氯仿与100mL甲醇作为溶剂,5滴N-乙基吗啉作为催化剂,75℃下回流反应48小时。反应结束后冷却至室温,减压蒸馏除去溶剂,拌样装柱,使用二氯甲烷与甲醇作为淋洗剂,减压蒸馏除去淋洗剂后得到红色固体即为目的产物86.0mg。收率为60%。核磁1H图为图6所示,核磁数据为:1H NMR(400MHz,MeOD)δ9.75(s,4H,A-tpy-H3’5’),9.50(s,1H,Ph-Ha),9.52(s,4H,B-tpy-H3’5’),9.25-9.23(d,4H,J=8Hz,A-tpy-H33”),9.10(s,2H,Ph-Hc),9.02-9.00(d,4H,J=8Hz,B-tpy-H33”),8.97(s,4H,C-tpy-H3’5’),8.83(s,2H,Ph-Hh),8.79-8.77(d,4H,J=8Hz,C-tpy-H33”,C-tpy-H66”),8.70(s,1H,Ph-Hb),8.55-8.52(d,2H,J=12Hz,Ph-Hd),8.39-8.36(d,2H,J=12Hz,Ph-He),8.32-8.27(m,4H,C-tpy-H44”),8.09-8.05(m,9H,A-tpy-H44”,B-tpy-H44”,Ph-Hp),7.72-7.69(m,8H,A-tpy-H66”,B-tpy-H66”),7.67-7.66(m,4H,Ph-Hf,Ph-Hg),7.58-7.55(m,4H,C-tpy-H55”),7.38-7.32(m,8H,A-tpy-H55”,B-tpy-H55”),3.75(s,6H,H-OMe).
多三联吡啶金属有机配体LA的合成:
将S9(30.0mg,0.01mmol),对三联吡啶苯硼酸(56.0mg,0.16mmol),加入100mL圆底烧瓶,加入70mL四氢呋喃作为溶剂,超声至固体完全溶解,碳酸钾(15.0mg,0.10mmol)溶于0.1mL水加入反应体系,迅速称量催化剂四三苯基膦钯(21.2mg,0.02mmol)加入反应体系,对装置进行氮气保护,75℃下加热搅拌回流反应48h。反应结束后,减压蒸馏除去溶剂,加入二氯甲烷和铝粉拌样装柱,以二氯甲烷和甲醇为淋洗剂,减压蒸馏除去溶剂得到红色固体,即为目的产物26.0mg,收率为70%。核磁1H图为图7所示,核磁数据为:1H NMR(500MHz,CD3CN)δ9.41(s,4H,A-tpy-H3’5’),9.30(s,4H,B-tpy-H3’5’),9.22(s,2H,Ph-Ha),9.08(s,6H,C-tpy-H3’5’,Ph-Hb),8.92(s,4H,D-tpy-H3’5’),8.92-8.81(m,28H,A-tpy-H33”,B-tpy-H33”,C-tpy-H33”D-tpy-H33”,C-tpy-H66”,D-tpy-H66”,Ph-Hc,h),8.51-8.43(m,8H,J=10Hz,Ph-He ,d,g,f),8.39-8.31(m,8H,A-tpy-H44”,B-tpy-H44”),8.22-8.21(d,4H,J=5Hz,Ph-Hj),8.12-8.11(d,4H,J=5Hz,Ph-Hk),8.07-8.03(m,8H,C-tpy-H44”,D-tpy-H44”),7.89(s,4H,Ph-Hi),7.60-7.58(m,8H,A-tpy-H66”,B-tpy-H66”),7.31-7.27(m,8H,C-tpy-H55”,D-tpy-H55”),3.56(s,6H,H-OMe).ESI-MS(分子式:C174H110F24N28O18Ru2S8):m/z 668.71[M–3PF6 -]3+(模拟值m/z:668.60),939.93[M–2PF6 -]2+(模拟值m/z:939.88).
五元花环状金属有机超分子的合成:
将多三联吡啶金属有机配体LA(式1:3.0mg,0.79μmol)投入到100mL圆底烧瓶中,用移液枪加入溶于乙二醇的金属离子FeCl2·4H2O(3.3mg,1.58μmol),加入45mL混合溶剂乙腈/乙二醇(v/v,2:1),在180±5℃反应12h。待冷却至室温后,加入过量的双三氟甲磺酸亚胺锂盐(NTf-)饱和甲醇溶液进行沉淀,通过抽滤,甲醇洗涤三次,得到红色固体产物5.8mg,收率为93.5%。核磁1H图为图8所示,核磁数据为:1H NMR(500MHz,CD3CN)δ9.49(s,20H,A-tpy-H3’5’),9.46(s,20H,B-tpy-H3’5’),9.40(s,20H,C-tpy-H3’5’),9.31(m,25H,D-tpy-H3’5’,Ph-Ha),9.22(s,5H,Ph-Hc),9.18(s,10H,Ph-Hb),9.08(s,5H,Ph-Hh),8.94-8.85(m,40H,A-tpy-H33”,B-tpy-H33”),8.79-8.75(m,20H,C-tpy-H33”),8.73-8.68(m,20H,D-tpy-H33”),8.67-8.63(m,20H,Ph-He,d,g,f),8.59-8.51(m,20H,Ph-Hj),8.34-8.30(m,20H,Ph-Hk),8.13-8.05(m,45H,A-tpy-H44”,B-tpy-H44”,Ph-Hj),8.02-7.93(m,40H,C-tpy-H44”,D-tpy-H44”),7.68-7.62(m,40H,A-tpy-H66”,B-tpy-H66”),7.38-7.27(m,80H,C-tpy-H66”,D-tpy-H66”,A-tpy-H55”,B-tpy-H55”),7.26-7.12(m,40H,C-tpy-H55”,D-tpy-H55”),3.66(s,30H,H-OMe).电喷雾质谱图为图9所示,质谱数据为ESI-MS(分子式:C910H550F240Fe10N160O170Ru10S80):m/z1653.72[M–13NTf-]13+(模拟值m/z:1653.61),1515.58[M–14NTf-]14+(模拟值m/z:1515.49),1395.48[M–15NTf-]15+(模拟值m/z:1395.78),1291.05[M–16NTf-]16+(模拟值m/z:1291.03),1198.67[M–17NTf-]17+(模拟值m/z:1198.61),1116.55[M–18NTf-]18+(模拟值m/z:1116.46),1042.99[M–19NTf-]19+(模拟值m/z:1042.95),976.94[M–20NTf-]20+(模拟值m/z:976.80),916.88[M–21NTf-]21+(模拟值m/z:916.94).
五元花环状金属有机超分子质谱分析:
将五元花环状金属有机超分子进行ESI-MS测试,得到一系列呈现正态分布的质谱峰,对应于该超分子从+23到+12电荷数的峰,如图9所示,其荷质比(m/z)分别为:1653.72,1515.58,1395.48,1291.05,1198.67,1116.55,1042.99,976.94,916.88,每一个峰完全对应于其丢失相应的NTf-阴离子。质谱数据很直接的提供了分子质量为25139Da的金属有机超分子组成:C910H550F240Fe10N160O170Ru10S80,既表明了组装产物是五聚物,包含对应的五倍配体与十倍金属Fe2+离子。ESI-MS谱图中没有其他组装结构的信号峰。通过ESI-MS表征可知,单一的金属有机五元花环Fe10LB5超分子(式A)结构被成功定量合成。
五元花环状金属有机超分子形貌分析:
透射电镜(TEM)是一种可以直接观察微观形貌的测试手段,使用透射电镜对聚合物进行观察。将超分子化合物溶于乙腈溶剂中,超声使其分散均匀(浓度为10-6mol/L),使用超薄碳支撑膜作为衬底,得到图像如图10,一系列的均匀分散的小球形貌,与模拟分子结构尺寸相符。
对比例1
和实施例1相比,区别仅在于,采用等摩尔量的CrCl34H2O替换所述的氯化亚铁,结果发现,无法获得所述的五元花状结构的超分子。
对比例2
和实施例1相比,区别仅在于,步骤(1)制备过程中,采用与2,7-二硼酸酯基萘(S2)类似的原料(2,8-二溴二苯并呋喃(A)或2,8-二溴二苯并噻吩(B)或2,7-二溴萘(C))与4’-硼酸三联吡啶进行suzuki-coupling反应但均未成功。
实施例2:
对实施例1制得的超分子(五元花环状金属有机超分子)进行凝胶化。将五元花环状金属有机超分子溶解在DMF中,且浓度为0.1mmol/ml,随后放置3~5天,获得凝胶。所述的凝胶的图片见图11,对凝胶的SEM表征见图12。图11中玻璃瓶倒置而内容物不流动,说明其成功凝胶化;图12说明胶体内部分子交联,形成了三维网状立体结构。
Claims (12)
7.一种权利要求6所述的五元花环状金属有机超分子的制备方法,其特征在于,将权利要求1所述的多三联吡啶金属有机配体化合物和M离子源在180±5℃下进行配位反应得到;
多三联吡啶金属有机配体化合物和M离子源的摩尔比为1:2。
8.如权利要求6所述的五元花环状金属有机超分子的制备方法,其特征在于,所述的M离子源为可溶性的亚铁源和/或锌源。
9.如权利要求6所述的五元花环状金属有机超分子的制备方法,其特征在于,配位反应的溶剂为乙腈和乙二醇的混合溶剂。
10.如权利要求6所述的五元花环状金属有机超分子的制备方法,其特征在于,配位反应的时间不低于8h。
11.如权利要求6所述的五元花环状金属有机超分子的制备方法,其特征在于,配位反应的时间为8~12h。
12.一种权利要求6所述的五元花环状金属有机超分子的应用,其特征在于,用作凝胶材料。
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