CN116478421B - 基于联萘酚骨架的手性金属框架材料及其制备方法和应用 - Google Patents
基于联萘酚骨架的手性金属框架材料及其制备方法和应用 Download PDFInfo
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- CN116478421B CN116478421B CN202310553465.9A CN202310553465A CN116478421B CN 116478421 B CN116478421 B CN 116478421B CN 202310553465 A CN202310553465 A CN 202310553465A CN 116478421 B CN116478421 B CN 116478421B
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- binaphthol
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Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6443—Fluorimetric titration
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Abstract
本发明涉及功能金属有机框架材料技术领域,尤其涉及基于联萘酚骨架的手性金属框架材料及其制备方法和应用,本发明所制备的单手性配体是一种全新的轴手性配体,所述的手性金属有机框架材料结构新颖且具有较高的水稳定性和较好的发光性能,能够与金属离子发生定量的荧光淬灭作用。同时,特定的手性孔道,还能与脯氨酸、精氨酸和1‑苯基乙醇发生主客体作用,实现对手性分子的荧光识别。因此,在水溶液中的硝基化合物和手性分子检测领域具有潜在的应用前景。
Description
技术领域
本发明涉及功能金属有机框架材料技术领域,尤其涉及基于联萘酚骨架的手性金属框架材料及其制备方法和应用。
背景技术
水中的有机污染物是导致环境污染的重要因素之一,通过食物链的富集作用对人类的健康产生了严重的威胁。常见的检测技术如色谱、核磁、质谱等都依赖复杂的操作和仪器,昂贵且耗时。基于荧光传感的检测技术为水溶液中有机化合物分子的识别和分离提供了一种简单有效、快速直接的方法。尽管离散型配合物作为荧光探针的化学传感研究取得了巨大的成功,但是合成上的困难以及难以回收利用等限制了其实际应用。因而,开发一种具有潜在实用性价值的荧光探针材料,是十分重要且具有挑战性的工作。
近年来,发光金属有机框架材料(MOFs)秉承晶态功能材料的结构可设计性、孔道可调性以及官能团易修饰性等特点,成为一种很有发展潜力的荧光探针材料。大多数情况下,利用发光MOFs材料进行特异性识别和分离的关键在于材料空腔与目标客体分子的优先相互作用。而这些与MOFs晶体功能紧密相关的结构,如稳定的结构、规则的孔道和较高的比表面积,也可以最大限度地促进MOFs材料对客体分子的动态响应,进而实现MOFs材料的高灵敏性和高选择性。然而,将发光MOFs材料在荧光检测中显示出的巨大潜力真正的转化为实际应用技术,还应该突破以下限制:1)摆脱传统溶剂热合成的限制,在较短时间、较低温度下,以简单的合成条件、较高产率合成MOFs材料;2)针对目标有机分子的特征,特别是手性化合物识别的具有特定结构的MOFs材料的定向合成;3)进一步改善制备的MOFs材料的发光性能,确保在对目标有机分子识别过程中荧光响应信号传输和放大的稳定性。根据框架化学的原理,配体的结构和配位形式,不仅对MOFs材料的结构起到决定性作用,而且对制备的MOFs材料的功能性质也具有重要影响。因此,配体的理性设计与选择是解决以上问题的一个重要突破口。
联萘酚骨架配体是一类具有轴手性的刚性配体,原料丰富廉价、易于功能化修饰且具有良好的光学性能,广泛应用于不对称识别、分离和催化等领域,利用联萘酚骨架配体开发一款具有荧光识别应用的金属有机框架材料具有良好的市场前景。
发明内容
本发明的目的在于提供一种新型的轴手性金属有机框架材料,其在水溶液中对硝基化合物和手性分子具有荧光识别应用。进一步的,本发明采取如下技术方案。
本发明的第一个方面提供了基于联萘酚骨架的手性金属框架材料的制备方法,所述制备方法包括如下步骤:
S1.将(S)-联萘酚(CAS:18531-99-2)、溴乙烷、碳酸钾与丙酮混合,在惰性气体氛围下,加热回流反应5-10h;反应结束后,冷却,除去部分溶剂后,加水稀释搅拌5-10h,过滤,蒸馏水洗涤,得到中间体1;反应式如下:
S2.将中间体1与有机溶剂混合,在低温下滴加液溴,滴加完毕后,恢复至室温进行反应;反应结束后,淬灭过量的溴,分离有机相,干燥、减压蒸馏得到粗产物,柱色谱分离提纯得到中间体2;反应式如下:
S3.将中间体2、4-吡啶硼酸、三水磷酸钾和催化剂作为原料加入溶剂中,在惰性气体氛围下,加热反应1-5天;反应结束后,减压蒸馏得到粗产物,柱色谱分离得到中间体3;反应式如下:
S4.将中间体3溶解于1,4-二氧六环中,滴加硝酸镉水溶液,静置,过滤洗涤,得到手性金属框架材料。
在一些实施方式中,所述有机溶剂可以选自本领域常用的种类,例如二氯甲烷、苯、甲苯、二甲苯、戊烷、己烷、辛烷、甲醇、乙醇、异丙醇、乙醚、环氧丙烷、醋酸甲酯、醋酸乙酯、醋酸丙酯、丙酮、甲基丁酮、甲基异丁酮、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚等,本发明实施例中优选二氯甲烷。
在一些实施方式中,所述中间体1与液溴的摩尔比为(0.5-1.5):(3-7)。
进一步的,所述中间体1与液溴的摩尔比为(0.5-1.0):(4-7),优选的,摩尔比为1:(4-7),更优选的,摩尔比为1:5。
申请人在探究中发现,液溴的添加量对本发明的手性金属框架材料的性质有重要影响,液溴含量过高会导致萘环上过度溴化,产物进一步转化,理想产物含量降低,收率减少,而含量过低又会使得底物反应不完全,副产物增多,产物混杂,加大分离难度,经大量探究实验发现,二者摩尔比为1:5时效果最佳。
在一些实施方式中,所述S2中低温为0±5℃。
进一步的,所述淬灭过量的溴的方式可以为本领域惯用的方式,包括但不限于用硫代硫酸钠水溶液淬灭。
进一步的,所述S2中柱色谱分离的洗脱液为石油醚/乙酸乙酯(体积比为100/1-10/1)。
进一步的,所述中间体2为白色固体,具体为{(S)-4,4’,6,6’-四溴-2,2’-二乙氧基-1,1’-联萘酚}。
在一些实施方式中,所述中间体2、4-吡啶硼酸(CAS:181219-01-2)、三水磷酸钾和催化剂的摩尔比为1:(4-8):(4-8):(0.1-0.3)。
进一步的,所述催化剂可以选自四(三苯基膦)钯、醋酸钯、二苯基磷二茂铁二氯化钯、二氯二(三苯基膦)钯中的至少一种。
进一步的,中间体2、4-吡啶硼酸、三水磷酸钾和催化剂的摩尔比为1:(5-7):(5-7):(0.1-0.3),优选的,摩尔比为1:(5-7):(5-7):0.2,最优选的,摩尔比为1:6:6:0.2。
中间体2、4-吡啶硼酸、三水磷酸钾和催化剂四者的含量比例在本发明中极为重要,其中任一物质的量过少,都会导致底物反应不充分,产物混杂,增加分离难度,降低产率;其中任意任一物质的量增大,则会增加合成成本。
进一步的,所述S3中的溶剂可以选自本领域常用的有机反应溶剂,包括但不限于N,N-二甲基甲酰胺。
在一些实施方式中,所述S3中加热反应的温度为100±5℃。
进一步的,所述S3中柱色谱分离的洗脱液为二氯甲烷/甲醇(体积比100/1-10/1)。
进一步的,所述中间体3为白色固体,具体为单手性配体(S)-L。
在一些实施方式中,所述中间体3与硝酸镉的摩尔比为(0.5-1.5):(3-7)。
进一步的,所述中间体3与硝酸镉的摩尔比为(1.0-1.5):(3-7),优选的,摩尔比为(1.0-1.5):(5-7),最优选的,摩尔比为1:5。
硝酸镉的含量过高会导致金属盐伴随MOFs材料一起析出,造成过度浪费,而含量过低又会导致配体结合不完全,MOFs材料结晶性变差,而且导致收率降低,申请人偶然探究发现,二者的摩尔比为1:5时能够将MOFs材料获得更好的结晶性和收率。
在一些实施方式中,所述S4中静置的温度为30-70℃。
在一些实施方式中,所述S4中静置的时间为2-8h。
在一些实施方式中,所述惰性气体包括但不限于氮气或氩气,也可以是二者的混合气体。
本发明的第二个方面提供了基于联萘酚骨架的手性金属框架材料,由上述制备方法得到,其结构式为[Cd(s-L)](NO3)2。
本发明的第三个方面提供了所述的基于联萘酚骨架的手性金属框架材料的应用,所述手性金属框架材料用于金属离子和手性分子荧光的识别。
与现有技术相比,本发明具有以下有益效果:
1.本发明所制备的单手性配体是一种全新的轴手性配体,所述的手性金属有机框架材料结构新颖且具有较高的水稳定性(在水中浸泡3天,晶体结晶性基本不变见,详见图10)和较好的发光性能,能够与金属离子发生定量的荧光淬灭作用。同时,特定的手性孔道,还能与脯氨酸、精氨酸和1-苯基乙醇发生主客体作用,实现对手性分子的荧光识别。因此,在水溶液中的硝基化合物和手性分子检测领域具有潜在的应用前景。
2.本发明以联萘酚配体为骨架分子,通过简单的功能化修饰,成功得到了一种新的吡啶基联萘酚类配体,并利用吡啶基团与金属离子特有的配位性,制备了一种基于联萘酚骨架的手性发光MOFs材料。该晶体材料的合成方法简单,反应条件温和,反应时间短,可以大规模制备,为水溶液中硝基化合物和一些手性分子提供了一种具有潜在使用价值的新的MOF基荧光探针材料。
3.本发明的制备方法简单,反应条件温和,晶体产率高,可大规模制备。
附图说明
图1为实施例1的S2中制备中间体2的氢谱图;
图2为实施例1的S2中制备中间体2的碳谱图;
图3为实施例1的S3中制备的中间体3(单手性配体(S)-L)的氢谱图;
图4为实施例1的S3中制备的中间体3(单手性配体(S)-L)的碳谱图;
图5为实施例1的S4中制备的手性金属有机框架材料的晶体结构图;
图6为实施例2中手性金属有机框架材料对水溶液中高锰酸根离子的荧光滴定实验数据图;
图7为实施例3中手性金属有机框架材料对水溶液中硝基化合的荧光滴定实验数据图;
图8为实施例4中手性金属有机框架材料对水溶液中脯氨酸的荧光滴定实验数据图;
图9为实施例5中手性金属有机框架材料对水溶液中1-苯基乙醇的荧光滴定实验数据图;
图10为实施例1制备的手性金属有机框架材料的模拟XRD图谱,材料活化后的XRD图谱和水中浸泡三天后的XRD图谱。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
本实施例提供了基于联萘酚骨架的手性金属框架材料的制备方法,包括以下步骤:
S1.将(S)-联萘酚(20.0g,70mmol)、碳酸钾(32.90g,238mmol)和溴乙烷(31.4mL,240mmol)作为原料,在氩气氛围下,加入300mL丙酮加热回流8h,薄层色谱检测反应进程;待反应结束后,冷却,减压除去部分溶剂后,加入2L蒸馏水搅拌6h,过滤,用水反复洗涤三次后,冷冻干燥,得到中间体1(24.0g,收率99%);
S2.将中间体1(6.84g,20.00mmol)作为原料,加入100mL二氯甲烷溶剂完全溶解,在冰水浴条件下滴加液溴(5.20mL,100.00mmol),滴加完毕后,恢复至室温(25℃)反应过夜(10h);反应结束后,用硫代硫酸钠水溶液淬灭过量的溴,二氯甲烷萃取(100mL)分离有机相,重复萃取3次,无水硫酸钠干燥,减压蒸馏出去溶剂得到粗产物,柱色谱分离(石油醚/乙酸乙酯,体积比为100:1)提纯得到中间体2,为白色固体(S)-4,4’,6,6’-四溴-2,2’-二乙氧基-1,1’-联萘酚(7.9g,收率60%)。1HNMR(400MHz,CDCl3,ppm):8.40(d,J=2Hz,2H),7.72(s,2H),7.30(dd,J1=2Hz,J2=9Hz,2H),6.93(d,J=9Hz,4H),4.07-4.01(m,4H),1.08(t,J=7Hz,6H).13C NMR(100MHz,CDCl3,ppm):154.11,132.99,130.54,129.38,128.83,127.27,122.43,120.32,119.18,119.14,65.30,14.80.
S3.将(S)-4,4’,6,6’-四溴-2,2’-二乙氧基-1,1’-联萘酚(6.58g,10.00mmol)、4-吡啶硼酸(12.30g,60.00mmol)、三水磷酸钾(9.34g,60.00mmol)和四(三苯基膦)钯催化剂(2.31g,2.00mmol)作为原料,加入100mLN,N-二甲基甲酰胺,在氩气气体氛围下,加热100℃反应3天;反应结束后,减压蒸馏除去溶剂得到粗产物,柱色谱分离(二氯甲烷/甲醇,体积比为100:1)得到中间体3,为白色固体,即单手性配体(S)-L(4.9g,收率75%)。1HNMR(400MHz,CDCl3,ppm):8.73(d,J=6Hz,4H),8.44(d,J=6Hz,4H),8.05(d,J=2Hz,2H),7.54(d,J=6Hz,4H),7.48(dd,J1=2Hz,J2=5Hz,2H),7.39(s,2H),7.37(d,J=5Hz,2H),7.32(d,J=6Hz,4H),4.09(q,J=7Hz,4H),1.09(t,J=7Hz,6H).13C NMR(100MHz,CDCl3,ppm):154.04,149.69,149.64,149.59,147.85,147.51,139.12,134.22,133.15,126.52,126.14,124.86,124.68,123.57,121.05,119.76,116.52,64.67,14.59.
S4.将单手性配体(S)-L(65.08mg,1.00mmol)溶解于15mL 1,4-二氧六环中,再小心地滴加1.0mL硝酸镉(5mol/L)水溶液,得到无色澄清溶液,在35℃的温度下,静置2h后,析出无色八面体状晶体,过滤洗涤,即可得到高质量的手性金属有机框架材料,其结构式为[Cd(s-L)](NO3)2。
制备得到的手性金属有机框架材料的结构如图5所示。所制备的手性金属有机框架材料结晶于六方手性空间P6422,不对称单元包含半个配体(S)-L,一个镉离子和一个硝酸根离子。Cd原子与四个桥联配体(S)-L的氮原子和两个硝酸根离子配位,采取拉长的八面体配位模式。配体(S)-L分别与四个Cd离子配位,其吡啶环沿着联萘的轴1,1’键旋转,且萘环与1,1’键之间的二面角为97.45°。四个不同方向的金属-吡啶链通过联萘配体的骨架桥联,在c轴方向上形成一个直径为9的手性孔道。
实施例2
本实施例提供了手性金属有机框架材料对高锰酸根离子的荧光滴定实验,实验结果见图6:
将实施例1中得到的手性金属有机框架材料充分研磨,称取1.8mg分散于2mL的蒸馏水中,超声20分钟,使其分散均匀。然后向悬浊液中滴加物质的量浓度为1×10-4mol/L的高锰酸钾的水溶液进行荧光检测。随着高锰酸钾溶液的滴加,制备的金属有机框架材料具有明显的荧光淬灭效应,并呈现较好的线性关系。利用Stern-Volmer公式计算可得Ksv=2.1×105M-1,并根据公式LOD=3σ/k,可得高锰酸根离子的检出限为3.5mM。
图6中左边为滴加高锰酸钾时的荧光滴定猝灭曲线,右边为Stern-Volmer拟合曲线,分析可知,Ksv数值结果。
实施例3
本实施例提供了手性金属有机框架材料对4-硝基苯甲酸的荧光滴定实验,实验结果见图7:
将实施例1中得到的手性金属有机框架材料充分研磨,称取1.8mg分散于2mL的蒸馏水中,超声20分钟,使其分散均匀。然后向悬浊液中滴加物质的量浓度为1×10-4mol/L的4-硝基苯甲酸的水溶液,进行荧光检测。随着4-硝基苯甲酸水溶液的滴加,制备的金属有机框架材料具有明显的荧光淬灭效应,并呈现较好的线性关系。利用Stern-Volmer公式计算可得Ksv=3.08×104M-1,并根据公式LOD=3σ/k,可得4-硝基苯甲酸的检出限为24mM。
图7中左边为荧光滴定猝灭曲线,右边为Stern-Volmer拟合曲线,分析可知,Ksv数值结果。
实施例4
本实施例提供了手性金属有机框架材料对D/L-脯氨酸的荧光滴定实验,实验结果见图8:
将实施例1中得到的手性金属有机框架材料充分研磨,称取1.8mg分散于2mL的蒸馏水中,超声20分钟,使其分散均匀。然后向悬浊液中滴加含有D-或L-对映体的脯氨酸的水溶液(1×10-3mol/L),进行荧光检测。随着D/L-脯氨酸溶液的滴加,制备的手性金属有机框架材料具有明显的荧光淬灭效应,同时由于手性孔道的作用,手性金属有机框架材料对L-脯氨酸的主客体作用更加明显。利用Stern-Volmer公式计算可得对映体选择性EF=1.69。
图8中左上为滴加D-脯氨酸时的荧光滴定淬灭曲线,右上为滴加L-脯氨酸时的荧光滴定淬灭曲线,下部分为Stern-Volmer拟合曲线,分析可知,Ksv数值结构以及对映选择性{Ksv(L)/Ksv(D)}
实施例5
本实施例提供了手性金属有机框架材料对R/S-1-苯基乙醇的荧光滴定实验,实验结果见图9:
将实施例1中得到的手性金属有机框架材料充分研磨,称取1.8mg分散于2mL的蒸馏水中,超声20分钟,使其分散均匀。然后向悬浊液中滴加含有R-或S-对映体的1-苯基乙醇的水溶液(1×10-3mol/L),进行荧光检测。随着1-苯基乙醇溶液的滴加,制备的手性金属有机框架材料具有明显的荧光淬灭效应,同时由于手性孔道的作用,手性金属有机框架材料对S-1-苯基乙醇的主客体作用更加明显。利用Stern-Volmer公式计算可得对映体选择性EF=1.55。
图9中左上为滴加R-1-苯基乙醇溶液时的荧光滴定曲线,右上为滴加S-1-苯基乙醇溶液时的荧光滴定曲线,下部分为Stern-Volmer拟合曲线,分析可知,Ksv数值结构以及对映选择性{Ksv(L)/Ksv(D)}。
综上所述,上述实施案例基于一种新的联萘酚类四齿有机配体与金属镉离子配位组装,制备的手性金属有机框架材料。X射线晶体衍射结果显示,本发明材料呈现拉长的八面体结构,内部具有一定的手性孔道,可以容纳一些有机小分子。一系列的荧光滴定实验结果显示,本发明材料的晶体孔道能够与对硝基苯甲酸等有机分子发生主客体化学作用,进而导致荧光淬灭现象。同时,手性孔道还能与氨基酸等手性分子进行特异性识别,且通过进一步的荧光滴定实验研究表明,本发明材料对其中一个对映体的结合力显著高于另一种对映体。本发明为水溶液中硝基化合物和手性分子的识别提供了一种简单可行的方法。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明所述原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.基于联萘酚骨架的手性金属框架材料的制备方法,其特征在于,所述制备方法包括如下步骤:
S1.将(S)-联萘酚、溴乙烷、碳酸钾与丙酮混合,在惰性气体氛围下,加热回流反应5-10h;反应结束后,冷却,除去部分溶剂后,加水稀释搅拌5-10h,过滤,蒸馏水洗涤,得到中间体1;反应式如下:
S2.将中间体1与有机溶剂混合,在低温下滴加液溴,滴加完毕后,恢复至室温进行反应;反应结束后,淬灭过量的溴,分离有机相,干燥、减压蒸馏得到粗产物,柱色谱分离提纯得到中间体2;反应式如下:
S3.将中间体2、4-吡啶硼酸、三水磷酸钾和催化剂作为原料加入溶剂中,在惰性气体氛围下,加热反应1-5天;反应结束后,减压蒸馏得到粗产物,柱色谱分离得到中间体3;反应式如下:
S4.将中间体3溶解于1,4-二氧六环中,滴加硝酸镉水溶液,静置,过滤洗涤,得到手性金属框架材料;
所述中间体1与液溴的摩尔比为1:5;
所述中间体2、4-吡啶硼酸、三水磷酸钾和催化剂的摩尔比为1:6:6:0.2;
所述中间体3与硝酸镉的摩尔比为1:5。
2.根据权利要求1所述的基于联萘酚骨架的手性金属框架材料的制备方法,其特征在于,所述S2中低温为0±5℃。
3.根据权利要求1所述的基于联萘酚骨架的手性金属框架材料的制备方法,其特征在于,所述S3中加热反应的温度为100±5℃。
4.根据权利要求1所述的基于联萘酚骨架的手性金属框架材料的制备方法,其特征在于,所述S4中静置的温度为30-70℃。
5.根据权利要求1所述的基于联萘酚骨架的手性金属框架材料的制备方法,其特征在于,所述S4中静置的时间为2-8h。
6.基于联萘酚骨架的手性金属框架材料,其特征在于,根据权利要求1-5任一项所述的制备方法得到。
7.根据权利要求6所述的基于联萘酚骨架的手性金属框架材料的应用,其特征在于,所述手性金属框架材料用于金属离子和手性分子的识别。
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