CN108884109A - 基于多向配体的有机金属复合物 - Google Patents
基于多向配体的有机金属复合物 Download PDFInfo
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- CN108884109A CN108884109A CN201780021140.9A CN201780021140A CN108884109A CN 108884109 A CN108884109 A CN 108884109A CN 201780021140 A CN201780021140 A CN 201780021140A CN 108884109 A CN108884109 A CN 108884109A
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Abstract
根据本发明,由化学式1表示的化合物的特征在于与金属离子配位,从而形成双向或多向有机金属复合物。因此,本发明可以利用胺‑醛缩合使用在能够合成各种配体的前体中,以及使用该前体的有机金属材料合成中。
Description
技术领域
相关申请的交叉引用
本申请要求于2016年07月29日在韩国知识产权局提交的韩国专利申请No.10-2016-0096905的权益,该申请的公开内容通过引用全部并入本说明书中。
本发明涉及一种用于制备金属-有机杂化结构的多向多齿配体和包含该配体的金属-有机杂化结构。
背景技术
席夫碱通过胺和醛的缩合来形成。席夫碱通常发现于生命系统中。例如,酶中间体的赖氨酸残基的胺官能团可逆地与辅因子或底物反应。此处,酶辅因子PLP与赖氨酸残基形成席夫碱,并且参与底物的转醛亚胺反应(transaldimidation reaction)。通过类似的机制,视黄醛辅因子与视紫质的赖氨酸残基形成席夫碱。
此外,席夫碱是配位化学中的一种代表性配体。氮供体原子兼具亲核性和路易斯碱性,并且同时也可以表现出π-受体性能。基于席夫碱模体(motif)的代表性多齿配体包括salen型配体。特别是,手性席夫碱已经广泛用作不对称催化的配体。当席夫碱用作多齿配体的骨架以支撑平面配位构型的金属中心时,可以构建具有无障碍通道以便于底物到达金属位点的多孔网络材料。
参与π-共轭的席夫碱也表现出各种光电性能。基于该性能,许多具有席夫碱官能团的复合材料被用作有机太阳能电池或钙钛矿太阳能电池的关键电子元件。此外,席夫碱的共价有机骨架(COF)正在成为利用胺-醛缩合反应的可逆性的下一代分子类材料。
为了充分利用席夫碱的独特的结构、化学和光电性能,正在积极进行制备以二维或三维网络结构连接的新骨架的研究。例如,根据最近报道的文献(R.Banerjee等人,J.Am.Chem.Soc.2016,138,2823-2828),作为D3h对称性分子的1,3,5-三甲酰基间苯三酚的醛基与具有位于三个方向上的胺基的胍缩合,以形成具有席夫碱连接的离子共价有机骨架。根据另一文献(P.Sun等人,Cryst.Engation.Des.2015,15,5360-5367),使用席夫碱缩合制备的配体与金反应以形成金属凝胶。
本发明人设计了由席夫碱衍生的多向配体以使金属-配体键的数量最大化,确认具有网络拓扑的金属-有机杂化结构通过与双向生长的多核重复单元的超分子相互作用而形成,并且完成了本发明。
发明内容
技术问题
本发明的一个目的是提供一种在它的结构和功能方面具有广泛的可扩展性的多向多齿配体化合物,用于制备金属-有机杂化结构。
本发明的另一目的是提供一种基于多向多齿配体的金属-有机杂化结构。
技术方案
本发明提供一种通过由下面的化学式1表示的化合物或它的盐与金属离子配位键合而形成的金属-有机杂化结构:
[化学式1]
在化学式1中,
R各自独立地是-R1、-NH-CO-R2、或-NH-R2,
R1各自独立地是-OH、C6-60芳基、C1-10烷基、或氨基酸残基,
R2是C1-10烷基、C6-60芳基、或含有N、O和S中的一种的C4-60杂芳基。
所述由化学式1表示的化合物是用于制备表现出多孔性、导电性和电致变色性的金属-有机杂化结构的化合物。
优选地,R1各自独立地是-OH、苯基、萘基、甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、叔戊基、新戊基、异戊基、仲戊基、3-戊基,或选自丙氨酸、半胱氨酸、天冬氨酸、谷氨酸、苯丙氨酸、组氨酸、异亮氨酸、赖氨酸、亮氨酸、甲硫氨酸、天冬酰胺、吡咯赖氨酸、谷氨酰胺、精氨酸、丝氨酸、苏氨酸、硒代半胱氨酸、缬氨酸、色氨酸和酪氨酸中的氨基酸残基。
氨基酸残基指在氨基酸的结构中除了氨基之外的结构。氨基与醛缩合以形成亚胺。例如,在丙氨酸的情况下,氨基酸残基是丙酸,丙酸是在丙氨酸的结构中除了氨基之外的结构。
此外,优选地,R2是甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、叔戊基、新戊基、异戊基、仲戊基、3-戊基、己基、辛基、苯基、萘基、或吡啶基。
此外,当由化学式1表示的化合物包含羧基时,它可以以盐的形式存在,其中,平衡离子可以是Na+、K+等。
由化学式1表示的化合物的代表性实例包括由下面的化学式1-1至化学式1-5表示的化合物:
[化学式1-1]
[化学式1-2]
[化学式1-3]
[化学式1-4]
[化学式1-5]
由化学式1表示的化合物具有联苯基支架,并且能够通过π-共轭进行电荷转移。此外,由化学式1表示的化合物在各个苯环上具有羟基,在羟基的邻位具有两个亚胺基。它可以通过这些羟基和亚胺基与金属离子配位。
特别地,由化学式1表示的化合物的特征在于,除了羟基和亚胺基之外,亚胺基上的取代基R可以具有可以另外与金属离子配位的R1取代基、酰亚胺键(-NH-CO-R2)、或胺基(-NH-R2)。因此,除了通过羟基和亚胺基与金属离子的配位键之外,还可以与金属离子进行另外的配位键合,因此,由化学式1表示的化合物和金属离子形成二维或三维网络结构。金属-有机杂化结构的网络结构的代表性实例示于图1中。
在本发明的金属-有机杂化结构中,由化学式1表示的化合物的有机配体和金属离子键合以形成网络结构。在这些材料中,具有结晶性的那些被称为MOF(金属-有机骨架),而没有结晶性的具有包埋溶剂的那些被称为凝胶。可以预期,在这种网络结构中,通过由化学式1表示的化合物的双酚骨架的π-共轭与配位的金属离子促进电荷传输。
此外,如上所述,网络中的电荷传输可以是双向的或多向的而不是单向的。因此,与仅能够通过π-共轭进行电荷传输的聚合物、或能够单向电荷传输的聚合物相比,在本发明的金属-有机杂化结构中,促进电荷转移,显著改善导电性,并且可以实现长距离电荷转移。此外,通过能够多电子转移的氧化还原活性过渡金属中心和氧化还原活性π-共轭配体之间的相互作用,可以实现仅用有机类导电聚合物难以实现的新的电性能。
对金属离子的金属没有具体限制,例如,可以包括诸如Tb、Eu、Yb等的镧系金属,以及诸如Ti、V、Mn、Fe、Co、Ni、Cu、Zn等的第1周期过渡金属,诸如Zr、Mo、Ru、Rh、Pd、Ag等的第2周期过渡金属,以及诸如Ir、Pt、Au等的第3周期过渡金属。
此外,金属-有机杂化结构可以通过混合上述由化学式1表示的化合物和金属前体来制备。此处,优选使用碱以使由化学式1表示的化合物可以被离子化,例如,可以使用胺(三乙胺)等。
根据本发明,凝胶形式的金属-有机杂化结构的特征在于在可见光波长区域中具有强吸收性的特征光跃迁,该光跃迁由电荷转移(CT)电子跃迁产生。特别是,即使在高温(约140℃)下也能保持凝胶形式,这是由于二维或三维网状结构通过由化学式1表示的化合物与金属离子的配位键而产生的金属-有机网络的稳定性导致的。
另外,由于该金属-有机杂化结构包含金属离子,因此它可以用作使用这些金属离子的催化剂。特别是,由于金属离子在金属-有机杂化结构中以规则的间隔排列,因此可以进一步提高催化活性。此外,由于光学性能根据金属离子的状态而改变,因此可以应用于使用它的各种传感器。此外,由于根据本发明的金属-有机杂化结构是多孔的,因此它可以用于气体分离或气体吸附。
本发明提供一种上述的由化学式1表示的化合物的制备方法,如下面的反应式1所示。
[反应式1]
具体地,所述制备方法包括以下步骤:使由化学式1'表示的化合物、由化学式2'表示的化合物和三氟乙酸反应以制备由化学式3'表示的化合物(步骤1);以及使由化学式3'表示的化合物与由化学式4'表示的化合物反应(步骤2)。
步骤1是达夫反应,其中,醛基取代在由化学式1'表示的化合物的羟基的邻位。
优选地,由化学式1'表示的化合物与由化学式2'表示的化合物的摩尔比为1:20。此外,三氟乙酸还起到溶剂的作用,并且优选使用使得它可以溶解由化学式1'表示的化合物和由化学式2'表示的化合物两者。
优选地,步骤1的反应温度为100℃至150℃。此外,优选地,步骤1的反应时间为1天至10天。
在步骤1的反应之后,可以进行得到产物的步骤。例如,可以将反应混合物加入到过量(1mol至5mol)的盐酸中,并搅拌1天至3天以得到沉淀物。为了纯化它,沉淀物可以用二甲基亚砜重结晶,以得到由化学式3'表示的化合物。
步骤2是醛和羟胺反应以形成醛肟,其中,醛肟在由化学式3'表示的化合物的醛基上形成。在由化学式4'表示的化合物中,R如化学式1中所定义。
作为步骤2的反应的溶剂,可以优选使用水、C1-4醇、或它们的混合溶剂,更优选水/乙醇混合溶剂或水/甲醇混合溶剂。
在步骤2的反应之后,可以进行得到产物的步骤。例如,可以加入过量的水以过滤产生的沉淀物,然后依次用水和丙酮洗涤,从而得到由化学式1表示的化合物。
此外,当得到凝胶形式的由化学式1表示的化合物时,根据需要,可以用超临界二氧化碳处理以除去溶剂。
有益效果
如上所述,根据本发明的由化学式1表示的化合物可以与金属离子配位以形成双向或多向的金属-有机杂化结构。因此,本发明可以提供使用胺-醛缩合能够合成各种配体的前体,并且使用该前体用于合成金属-有机材料。
附图说明
图1示出了通过根据本发明的一个实施方案的化合物与金属离子的配位键形成的网络结构;
图2示出了本发明的金属-有机杂化结构制备为凝胶形式;
图3示出了测量本发明的金属-有机杂化结构(铽(III)金属凝胶)的荧光的结果(固体荧光,吸收波长=450nm,最大发射波长=629nm,基线校正);
图4示出了用SEM观察本发明的金属-有机杂化结构(钴(II)金属凝胶)的表面的结果;
图5示出了用SEM观察本发明的金属-有机杂化结构(镍(II)金属凝胶)的表面的结果;
图6示出了将本发明的金属-有机杂化结构制备为干凝胶的结果;
图7至图14示出了将本发明的金属-有机杂化结构制备为干凝胶,并且用SEM观察表面的结果;
图15至图23示出了将本发明的金属-有机杂化结构制备为干凝胶,并且用EDS(能量色散X射线光谱)观察样品中各个元素的含量和分布的结果。
具体实施方式
在下文中,为了更好地理解本发明,提供了优选的实施例。然而,提供这些实施例仅用于说明本发明,并且本发明的范围不限于此。
实施例1
(步骤1)
将HMTA(环六亚甲基四胺,7.530g,53.70mmol)加入到干燥的圆底烧瓶中。用氩气吹扫烧瓶,并且加入TFA(三氟乙酸,50mL)。在完全溶解HMTA后,迅速加入联苯-4,4'-二醇(1.000g,5.370mmol)。在确认混合物变成橙色后,将混合物在120℃下加热7天。产物为深红色,并且将其倒入到4N的HCl(100mL)中以分离黄色沉淀。沉淀物用热DMSO重结晶,得到2.460g的黄色微晶(产率:65.1%)。
(步骤2)
将在步骤1中制备的化合物(0.296g,1.000mmol)和NH2OH-HCl(0.420g,6.0mmol)加入到反应器中。加入水(7mL)后,将混合物加热至80℃。逐滴加入甲醇直至混合物变得透明。紧密密封反应器后,将混合物在100℃下加热1小时。冷却至室温后,加入水以诱导沉淀。通过过滤分离固体物质,并且用水洗涤,得到淡黄色产物(粉末,0.360g)。
1H NMR(300MHz,DMSO-d)δ11.60(s,4H),10.88(s,2H),8.45(s,4H),7.83(s,4H)
实施例2
将氢氧化钾(6.80mmol,0.38g)和10mL的乙醇加入到反应器中并搅拌。在搅拌下将甘氨酸(6.80mmol,0.510g)加入到混合物中,搅拌混合物直至固体物质完全溶解。单独制备10mL的乙醇中分散有实施例1的步骤1中制备的四甲酰基联苯酚(1.70mmol,0.500g)的混合物,然后在搅拌下将其缓慢加入到反应器中。在添加过程中,混合物变红。完成添加后,将混合物倒入到20mL的水中,然后过滤以除去未溶解的固体物质。在减压下除去水后,将剩余的物质分散在二甲基甲酰胺的溶剂中并过滤,得到橙色粉末形式的产物(0.4654g,74.6%)。
1H NMR(300MHz,D2O)δ3.31(s,8H),7.91(s,4H)
实施例3
将13mL的乙醇加入到含有在实施例1的步骤1中制备的四甲酰基联苯酚(0.500g,1.678mmol)的反应器中。在搅拌混合物的同时,用注射器加入苯肼(0.726g,6.710mmol)。将反应器密封并在100℃下加热8小时。将反应混合物冷却至室温,然后倒入到100mL的水中。通过过滤分离所得的沉淀物,用丙酮洗涤,得到黄色粉末形式的产物(0.7797g,70.6%)。
LC-MS:计算C40H34N8O2的[M]+为658.28,实测659.4
实施例4
将在实施例1的步骤1中制备的四甲酰基联苯酚(0.500g,1.678mmol)和烟酰肼(0.920g,6.710mmol)加入到反应器中,并向其中加入13mL的乙醇。将反应器密封并在100℃下加热8小时。将反应混合物冷却至室温,然后倒入到100mL的水中。通过过滤分离沉淀物,用丙酮洗涤,得到黄色粉末形式的产物(0.8971g,69.1%)。
MALDI-TOF:计算C40H30N12O6的[M]+为774.24,实测775.5
实施例5
将在实施例1的步骤1中制备的四甲酰基联苯酚(0.500g,1.678mmol)和正辛酰肼(1.062g,6.710mmol)加入到反应器中,并向其中加入13mL的乙醇。将反应器密封并在100℃下加热8小时。将反应混合物冷却至室温,然后倒入到100mL的水中。通过过滤分离沉淀物,用丙酮洗涤,得到黄色粉末形式的产物(0.8072g,56.0%)。
LC-MS:计算C48H74N8O6的[M]+为858.57,实测859.7
实验实施例1:凝胶的制备
1)实验实施例1-1
将在实施例1中制备的化合物(50.0mg,0.140mmol)加入到瓶中,加入DMF(1.0mL)使其溶解。滴加三乙胺(0.12mL,0.840mmol)并确认溶液变为橙色后,迅速加入下面的表1的物质。将混合物搅拌5秒后,将其加热至100℃以形成凝胶,在此过程中逐渐形成凝胶。
[表1]
2)实验实施例1-2
将在实施例1中制备的化合物(50.0mg,0.140mmol)加入到瓶中,加入DMF(1.0mL)使其溶解。在其完全溶解后,加入下面的表2的物质。此后,迅速滴加三乙胺(0.12mL,0.840mmol),加入后立即形成黑色凝胶。将混合物搅拌5秒后,将其加热至100℃以使凝胶均匀化并提高其强度。约1小时后,完成凝胶化过程。
[表2]
实验实施例1-2 | 溶解在DMF(3.0mL)中的FeCl2(90.0mg,0.240mmol) |
3)实验实施例1-3至1-6
将在实施例1中制备的化合物(50.0mg,0.140mmol)加入到瓶中,并在其中加入DMF(1.0mL)使其溶解。滴加三乙胺(0.12mL,0.840mmol)并确认溶液变为橙色后,迅速加入下面的表3的物质。加入后立即开始形成凝胶。将混合物搅拌5秒后,将其加热至100℃以使凝胶均匀化并提高其强度。约1小时后,完成凝胶化过程。
[表3]
实验实施例1-3 | 溶解在DMF(3.0mL)中的Co(OAc)2·4H2O(90.0mg,0.280mmol) |
实验实施例1-4 | 溶解在DMF(3.0mL)中的Ni(OAc)2·4H2O(140.0mg,0.420mmol) |
实验实施例1-5 | 溶解在DMF(3.0mL)中的Cu(OAc)2·H2O(140.0mg,0.420mmol) |
实验实施例1-6 | 溶解在DMF(3.0mL)中的Zn(OAc)2·2H2O(140.0mg,0.420mmol) |
在实验实施例1-1、1-3、1-4和1-6中制备的各个凝胶示在图2中。如图2所示,各个金属-有机杂化结构以凝胶形式制备。
4)实验实施例1-7至1-10
将在实施例1中制备的化合物(50.0mg,0.140mmol)加入到瓶中,加入DMF(1.0mL)使其溶解。滴加在1.0mL的乙醇中的甲醇钠(22.5mL,0.420mmol)的溶液,确认溶液变成橙色后,迅速加入下面的表4的物质。加入后立即开始形成凝胶。将混合物搅拌5秒后,将其加热至100℃以使凝胶均匀化并提高其强度。约1小时后,完成凝胶化过程。
[表4]
实验实施例1-7 | 溶解在DMF(3.0mL)中的Pd(OAc)2(95.0mg,0.420mmol) |
实验实施例1-8 | 溶解在DMF(3.0mL)中的Ru(acac)3(113.0mg,0.280mmol) |
实验实施例1-9 | 溶解在DMF(3.0mL)中的Tb(NO3)3·5H2O(122.0mg,0.280mmol) |
实验实施例1-10 | 溶解在DMF(3.0mL)中的Eu(NO3)3·5H2O(119.0mg,0.280mmol) |
实验实施例2:凝胶的荧光的测量
将在实验实施例1-9中制备的凝胶涂布在载玻片上,然后在80℃的真空烘箱中干燥2小时。测量干燥的凝胶的荧光光谱,激发波长为450nm,最大发射波长为629nm,如图3中所示。
实验实施例3:观察凝胶的SEM图像
1)实验实施例3-1
将在实验实施例1-3中制备的钴凝胶在真空下干燥12小时,并使用该产物得到SEM图像。具体地,将干燥的凝胶分散在粘附有碳双面胶带的测试桩上并用铂涂覆,并且在15kV的电压条件下观察。结果如图4中所示。
2)实验实施例3-2
将在实验实施例1-4中制备的镍凝胶在真空下干燥12小时,并使用该产物得到SEM图像。具体地,将干燥的凝胶分散在粘附有碳双面胶带的测试桩上并用铂涂覆,并且在5kV至15kV的电压条件下观察。结果如图5中所示。
实验实施例4:干凝胶的制备
用超临界二氧化碳处理在实验实施例1-2至1-10中制备的凝胶以除去溶剂,从而制备干凝胶。具体而言,将上述制备的凝胶装入由不锈钢制成的圆筒中,然后将其安装在超临界二氧化碳装置内。在40℃下,200atm的超临界二氧化碳以0.1mL/分钟的速度流动以除去溶剂,从而得到粉末形式的产物。用肉眼观察它们的一部分的结果示于图6中。
实验实施例5:干凝胶的分析
使用在实验实施例4中制备的干凝胶,得到SEM图像。具体地,将干凝胶分散在粘附有碳双面胶带的测试桩上并用铂涂覆,并且在5kV至15kV的电压条件下观察,结果示于图7至图15中。同时,通过EDS(能量色散X射线光谱法)测量干凝胶表面的元素分布,结果示于图16至图23中。各个图的内容如下面的表5所述。
[表5]
Claims (6)
1.一种金属-有机杂化结构,该金属-有机杂化结构通过由下面的化学式1表示的化合物或它的盐与金属离子配位键合而形成:
[化学式1]
在化学式1中,
R各自独立地是-R1、-NH-CO-R2、或-NH-R2,
R1各自独立地是-OH、C6-60芳基、C1-10烷基、或氨基酸残基,
R2是C1-10烷基、C6-60芳基、或含有N、O和S中的一种的C4-60杂芳基。
2.根据权利要求1所述的金属-有机杂化结构,其中,R1各自独立地是-OH、苯基、萘基、甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、叔戊基、新戊基、异戊基、仲戊基、3-戊基,或选自丙氨酸、半胱氨酸、天冬氨酸、谷氨酸、苯丙氨酸、组氨酸、异亮氨酸、赖氨酸、亮氨酸、甲硫氨酸、天冬酰胺、吡咯赖氨酸、谷氨酰胺、精氨酸、丝氨酸、苏氨酸、硒代半胱氨酸、缬氨酸、色氨酸和酪氨酸中的氨基酸残基。
3.根据权利要求1所述的金属-有机杂化结构,其中,R2是甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、叔戊基、新戊基、异戊基、仲戊基、3-戊基、己基、辛基、苯基、萘基、或吡啶基。
4.根据权利要求1所述的金属-有机杂化结构,其中,所述由化学式1表示的化合物是由下面的化学式1-1至化学式1-5中的一种表示的化合物:
[化学式1-1]
[化学式1-2]
[化学式1-3]
[化学式1-4]
[化学式1-5]
5.根据权利要求1所述的金属-有机杂化结构,其中,所述金属离子的金属是第1周期过渡金属、第2周期过渡金属、第3周期过渡金属、或镧系金属。
6.根据权利要求1所述的金属-有机杂化结构,其中,所述金属离子的金属是Ti、V、Mn、Fe、Co、Ni、Cu、Zn、Zr、Mo、Ru、Rh、Pd、Ag、Ir、Pt、Au、Tb、Eu、或Yb。
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Cited By (6)
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CN110157008A (zh) * | 2019-06-25 | 2019-08-23 | 哈尔滨理工大学 | 一种亚胺键联接的双孔共价有机骨架材料及其制备与应用 |
CN110229347A (zh) * | 2019-06-25 | 2019-09-13 | 哈尔滨理工大学 | 一种金属螯合的双孔共价有机骨架材料及其制备与应用 |
CN110229347B (zh) * | 2019-06-25 | 2021-10-01 | 哈尔滨理工大学 | 一种金属螯合的双孔共价有机骨架材料及其制备与应用 |
CN112174883A (zh) * | 2020-10-29 | 2021-01-05 | 西北师范大学 | 一种能单一选择性识别l-精氨酸的荧光传感器的合成及应用 |
CN112209849A (zh) * | 2020-10-29 | 2021-01-12 | 西北师范大学 | 一种能单一选择性识别甲苯的荧光传感器的合成及应用 |
CN112174883B (zh) * | 2020-10-29 | 2022-05-03 | 西北师范大学 | 一种能单一选择性识别l-精氨酸的荧光传感器的合成及应用 |
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