CN113214144B - 基于偶极有机配体的金属有机框架材料、合成方法及其应用 - Google Patents

基于偶极有机配体的金属有机框架材料、合成方法及其应用 Download PDF

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CN113214144B
CN113214144B CN202110527889.9A CN202110527889A CN113214144B CN 113214144 B CN113214144 B CN 113214144B CN 202110527889 A CN202110527889 A CN 202110527889A CN 113214144 B CN113214144 B CN 113214144B
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周杰
唐卫华
王俊杰
程尧
杨琳强
曹金如
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Nanjing University of Science and Technology
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Abstract

本发明公开了一种基于偶极有机配体的金属有机框架材料、合成方法及其应用。本发明所述的偶极有机配体的结构式为
Figure DDA0003066637210000011
其中,R1基团为电子受体基团,选自羰基、氰基、罗丹宁或茚酮等;Ar基团为MOF连接基团,选自吡啶、咪唑、吡唑或嘧啶等。通过偶极有机配体、联苯二甲酸和硝酸锌的溶剂热反应制备基于偶极有机配体的金属有机框架材料。本发明利用特殊结构的具有偶极矩的有机配体制备具有偶极活性位点的金属有机框架材料,制得的MOF材料具有良好的结晶性、热稳定性好和荧光量子产率,可以实现对硝基芳族爆炸物和新型爆炸物的选择性识别。

Description

基于偶极有机配体的金属有机框架材料、合成方法及其应用
技术领域
本发明涉及一种基于偶极有机配体的金属有机框架材料、合成方法及其在荧光检测爆炸物中的应用,属于分析化学领域。
背景技术
金属有机框架材料(Metal-organic frameworks,MOF)是一类由金属离子或团簇和有机配体通过配位键自组装而成的、具有高表面积的多孔材料。MOF的永久孔隙率和可调的孔径使其具有大的比表面积和活性位点,能够与客体分子之间发生相互作用,也可以通过改变有机连接体的官能团来改变MOF的化学选择性和灵敏度。同时,大多数MOF都具有良好的温度和湿度稳定性,因此基于MOF材料的化学传感具有广泛的应用前景。
目前,基于功能材料的光学传感已成为爆炸物检测的新方法。特定尺寸的分子可以进入到MOF内部的空腔中,与MOF结构中存在的活性位点或者官能团发生相互作用,轻松改变MOF的电子结构,从而可以改变MOF的光物理行为(发射,吸收和光致发光),即可以将要检测的爆炸性化合物的浓度转换为材料光学特性的变化。而精心设计的有机配体是制备预期的金属有机骨架材料的关键步骤。目前,偶极金属有机框架材料已经在烷烃的分离纯化中体现出一定的优势,而在荧光探测材料中,设计具有电子给体-受体(D-A)结构的化合物也正在成为设计敏感传感器的一种方法。由于具有高电子密度的大共轭平面的有机骨架非常敏感,可以容易吸引缺电子的硝基化合物,而强大的D-A结构可以导致电荷从给体基团转移到受体基团,并产生一个偶极矩。通过偶极-偶极相互作用,MOF材料可以选择性地检测出缺电子的硝基化合物,例如偶极矩为4.58D硝基苯(NB)。通过荧光MOF材料和爆炸物分子之间的客体-主体相互作用,发生荧光猝灭,实现对爆炸物的探测。其中,荧光MOF的偶极有机配体的设计直接影响了MOF对爆炸物的选择性识别能力及灵敏度。因此通过化学的手段、设计合成偶极有机配体及其金属有机框架材料是选择性识别爆炸物的一种方法。
发明内容
本发明提供一种基于芴单元的偶极有机配体,其结构式如下:
Figure BDA0003066637190000011
其中,R1基团为电子受体基团,选自羰基、氰基、罗丹宁或茚酮等;Ar基团为MOF连接基团,选自吡啶、咪唑、吡唑或嘧啶等。
本发明还提供上述基于芴单元的偶极有机配体的合成方法,包括以下步骤:
R1基团为羰基的偶极有机配体的制备:2,7-二溴-9-芴酮与杂芳基硼酸酯进行偶联反应,制备R1基团为羰基的偶极有机配体,反应式如下:
Figure BDA0003066637190000021
羰基被其他受体基团取代的偶极有机配体的制备:以R1基团为羰基的偶极有机配体继续与含受体基团的化合物发生加成反应,得到羰基被其他受体基团取代的偶极有机配体,反应式如下:
Figure BDA0003066637190000022
进一步地,上述基于芴单元的偶极有机配体的合成方法,具体步骤如下:
R1基团为羰基的偶极有机配体的制备:将2,7-二溴-9-芴酮和杂芳基硼酸酯溶于有机溶剂中,然后加入碱溶液,惰性气氛下加入Pd催化剂,80-120℃搅拌下进行偶联反应,反应结束后,冷却至室温,萃取有机相,并用无水Mg2SO4干燥,减压除去溶剂,纯化得到R1基团为羰基的偶极有机配体;
羰基被其他受体基团取代的偶极有机配体的制备:将R1基团为羰基的偶极有机配体和含R1基团的化合物溶于极性溶剂中,90-130℃搅拌下进行加成反应,反应结束后,洗涤过滤,真空干燥,得到官能团化的偶极有机配体。
优选地,所述的2,7-二溴-9-芴酮和杂芳基硼酸酯的摩尔比为1:2.05-3,优选为1:2.5。
优选地,有机溶剂选自甲苯、四氢呋喃,二氧六环或N,N-二甲基甲酰胺。
优选地,所述的碱选自K2CO3,Na2CO3或CsCO3,碱溶液的浓度为2M。
优选地,偶联反应的反应温度为90℃,反应时间为24小时。
优选地,所述的Pd催化剂选自四三苯基膦钯、醋酸钯或四(二亚苄基丙酮)二钯,Pd催化剂的摩尔量为2,7-二溴-9-芴酮的0.05倍。
优选地,惰性气氛为氮气。
优选地,极性溶剂选自醋酸、甲苯、二甲基亚砜或N,N-二甲基甲酰胺。
优选地,所述反应的反应时间为2-48小时,优选为12小时。
优选的,加成反应的反应温度为110℃。
本发明还提供基于上述偶极有机配体的金属有机框架材料,通过以下步骤合成:
将基于芴单元的偶极有机配体、辅助配体联苯二甲酸和金属源硝酸锌溶于N,N-二甲基甲酰胺中,80-140℃溶剂热反应,反应结束后,洗涤过滤,得到基于偶极有机配体的金属有机框架材料。
优选地,所述的溶剂热反应的反应温度为100℃。
优选地,所述的溶剂热反应的反应时间为48h。
优选地,所述的金属源、辅助配体和偶极有机配体的摩尔比为1:1:0.5-1。
更进一步地,本发明提供上述基于偶极有机配体的金属有机框架材料在荧光检测爆炸物中的应用。
进一步地,所述的爆炸物选自硝基苯类、硝基苯酚类或二氨基二硝基乙烯类(Fox-7)化合物。
具体地,所述的爆炸物包括但不限于以下化合物:
Figure BDA0003066637190000031
上述应用的具体方法为:
基于偶极有机配体的金属有机框架材料加入极性溶剂中制成MOF悬浮液,加入待测爆炸物溶液,检测其荧光发射光谱,根据荧光强度与爆炸物浓度的对应关系,确定爆炸物的类型和浓度。
优选地,MOF悬浮液的浓度为0.5mg/ml。
优选地,极性溶剂为水、甲醇、乙醇、乙腈、二氯甲烷、丙酮或N,N-二甲基甲酰胺等。
与现有技术相比,本发明的具有以下优点:
(1)本发明提供的有机配体具有大的共轭结构和给电子骨架,可以增强MOF的荧光强度和探测灵敏度;
(2)官能团化的有机配体具有独特的活性位点,可以提供多种分子间作用,提高爆炸物检测的选择性和灵敏性;
(3)利用由分子结构的高极性引起的MOF材料和爆炸物分子间的强烈主客体相互作用,导致MOF材料电荷密度变化和与爆炸物分子的结合能变化,辅之以光诱导电子转移与共振能量转移,实现荧光猝灭,实现爆炸物的探测。
附图说明
图1为实施例1中金属源、辅助配体和偶极有机配体不同比例下合成偶极MOF的XRD谱图。
图2为实施例2制备的偶极MOF对爆炸物TzFOX的灵敏性荧光检测谱图。
图3为实施例2制备的偶极MOF对爆炸物TzFox的探测的检出限结果图。
图4为实施例2制备的偶极MOF对不同种类爆炸物的检测能力测试图。
具体实施方式
下面结合实施例和附图对本发明作进一步详述。
实施例1
金属源、辅助配体和偶极有机配体不同比例下制备偶极MOF:
1.偶极有机配体的合成:在二颈烧瓶中,将2,7-二溴-9-芴酮(1.0g,2.96mmol),4-(3,3,4,4-四甲基硼烷-1-基)吡啶(1.52g,7.40mmol)溶解在甲苯(40mL)中,向其中加入2MK2CO3溶液(10mL)。将混合物用N2流脱气20分钟,并在N2气氛中加入Pd(PPh3)4(171mg,0.05mmol)。将混合物在氮气下于90℃搅拌24小时。然后将混合物冷却至室温,并用CH2Cl2萃取,并用无水Mg2SO4干燥,减压除去溶剂。固体通过柱色谱法纯化,得到偶极有机配体(产率:650mg,66%)。
2.偶极MOF的合成:
(1)Zn(NO3)2:联苯二甲酸:偶极有机配体=1:2:2比例下MOF1的合成:将Zn(NO3)2·6H2O(0.1mmol),联苯二甲酸(0.2mmol)和偶极有机配体(0.2mmol)溶解在10mLDMF中。将反应混合物超声处理半小时,直到反应物完全分散溶解。然后将其转移到反应釜中,在100℃下反应48h,冷却至室温。过滤固体产物并用DMF洗涤3遍,得到材料。
(2)Zn(NO3)2:联苯二甲酸:偶极有机配体=1:1:1比例下MOF2的合成:将Zn(NO3)2·6H2O(0.2mmol),联苯二甲酸(0.2mmol)和偶极有机配体(0.2mmol)溶解在10mLDMF中。将反应混合物超声处理半小时,直到反应物完全分散溶解。然后将其转移到反应釜中,在100℃下反应48h,冷却至室温。过滤固体产物并用DMF洗涤3遍,得到材料。
(3)Zn(NO3)2:联苯二甲酸:偶极有机配体=2:2:1比例下MOF3的合成:将Zn(NO3)2·6H2O(0.2mmol),联苯二甲酸(0.2mmol)和偶极有机配体(0.1mmol)溶解在10mLDMF中。将反应混合物超声处理半小时,直到反应物完全分散溶解。然后将其转移到反应釜中,在100℃下反应48h,冷却至室温。过滤固体产物并用DMF洗涤3遍,得到材料。
采取上述方法制备的偶极MOF的粉末XRD如图1所示,表明不同比例金属源、辅助配体和偶极有机配体合成的偶极MOF保持着相同的晶体结构,且具有良好结晶性。
实施例2
含吡啶芳基的偶极MOF的制备
合成路线为:
Figure BDA0003066637190000051
偶极有机配体的合成:在二颈烧瓶中,将2,7-二溴-9-芴酮(1.0g,2.96mmol),4-(3,3,4,4-四甲基硼烷-1-基)吡啶(1.52g,7.40mmol)溶解在甲苯(40mL)中,向其中加入2MK2CO3溶液(10mL)。将混合物用N2流脱气20分钟,并在N2气氛中加入Pd(PPh3)4(171mg,0.05mmol)。将混合物在氮气下于90℃搅拌24小时。然后将混合物冷却至室温,并用CH2Cl2萃取,并用无水Mg2SO4干燥,减压除去溶剂。固体通过柱色谱法纯化,得到偶极有机配体(产率:650mg,66%)。
MOF的合成:将Zn(NO3)2·6H2O(59.5mg,0.2mmol),联苯二甲酸(48.4mg,0.2mmol)和偶极有机配体(33.4mg,0.1mmol)溶解在10mLDMF中。将反应混合物超声处理半小时,直到反应物完全分散溶解。然后将其转移到反应釜中,在100℃下反应48h,冷却至室温。过滤固体产物并用DMF洗涤3遍,得到材料。
实施例3
含咪唑基团的偶极MOF的制备:
合成路线为:
Figure BDA0003066637190000061
偶极有机配体的合成:在二颈烧瓶中,将2,7-二溴-9-芴酮(1.0g,2.96mmol),咪唑-2-硼酸(0.83g,7.40mmol)溶解在甲苯(40mL)中,向其中加入2MK2CO3溶液(10mL)。将混合物用N2流脱气20分钟,并在N2气氛中加入Pd(PPh3)4(171mg,0.05mmol)。将混合物在氮气下于90℃搅拌24小时。然后将混合物冷却至室温,并用CH2Cl2萃取,并用无水Mg2SO4干燥,减压除去溶剂。固体通过柱色谱法纯化,得到偶极有机配体(产率:550mg,56%)。
MOF的合成:将Zn(NO3)2·6H2O(59.5mg,0.2mmol),联苯二甲酸(48.4mg,0.2mmol)和偶极有机配体(62.4mg,0.2mmol)溶解在10mLDMF中。将反应混合物超声处理半小时,直到反应物完全分散溶解。然后将其转移到反应釜中,在100℃下反应48h,冷却至室温。过滤固体产物并用DMF洗涤3遍,得到材料。
实施例4
含嘧啶芳基的偶极MOF的制备
合成路线为:
Figure BDA0003066637190000062
偶极有机配体的合成:在二颈烧瓶中,将2,7-二溴-9-芴酮(1.0g,2.96mmol),嘧啶-5-硼酸嚬哪醇酯(1.52g,7.40mmol)溶解在甲苯(40mL)中,向其中加入2MK2CO3溶液(10mL)。将混合物用N2流脱气20分钟,并在N2气氛中加入Pd(PPh3)4(171mg,0.05mmol)。将混合物在氮气下于90℃搅拌24小时。然后将混合物冷却至室温,并用CH2Cl2萃取,并用无水Mg2SO4干燥,减压除去溶剂。固体通过柱色谱法纯化,得到偶极有机配体(产率:620mg,63%)。
MOF的合成:将Zn(NO3)2·6H2O(59.5mg,0.2mmol),联苯二甲酸(48.4mg,0.2mmol)和偶极有机配体(33.4mg,0.1mmol)溶解在10mLDMF中。将反应混合物超声处理半小时,直到反应物完全分散溶解。然后将其转移到反应釜中,在100℃下反应48h,冷却至室温。过滤固体产物并用DMF洗涤3遍,得到材料。
实施例5
含氰基基团的偶极MOF的制备:
合成路线为:
Figure BDA0003066637190000071
R1基团为羰基的偶极有机配体的合成:在二颈烧瓶中,将2,7-二溴-9-芴酮(1.0g,2.96mmol),4-(3,3,4,4-四甲基硼烷-1-基)吡啶(1.52g,7.40mmol)溶解在甲苯(40mL)中,向其中加入2MK2CO3溶液(10mL)。将混合物用N2流脱气20分钟,并在N2气氛中加入Pd(PPh3)4(171mg,0.05mmol)。将混合物在氮气下于90℃搅拌24小时。然后将混合物冷却至室温,并用CH2Cl2萃取,并用无水Mg2SO4干燥,减压除去溶剂。固体通过柱色谱法纯化,得到R1基团为羰基的偶极有机配体(产率:580mg,58%)。
R1基团为羰基的偶极有机配体的官能团化:将R1基团为羰基的偶极有机配体(500mg,1.50mmol)和丙二腈(148mg,2.24mmol)的混合物在无水DMSO(10mL)中110℃加热反应5h。反应结束后,将产物滤出并用乙腈洗涤,在60℃下真空干燥,得到官能团化的偶极有机配体(产率:534mg,93%)。
MOF的合成:将Zn(NO3)2·6H2O(59.498mg,0.2mmol),联苯二甲酸(48.446mg,0.2mmol)和偶极有机配体(33.438mg,0.1mmol)溶解在10mLDMF中。将反应混合物超声处理半小时,直到反应物完全分散溶解。然后将其转移到反应釜(或密封小瓶)中,在100℃下反应48h,冷却至室温。过滤固体产物并用DMF洗涤3遍,得到MOF产物。
实施例6
含罗丹宁基团的偶极MOF的制备:
合成路线为:
Figure BDA0003066637190000072
R1基团为羰基的偶极有机配体的合成:在二颈烧瓶中,将2,7-二溴-9-芴酮(1.0g,2.96mmol),4-(3,3,4,4-四甲基硼烷-1-基)吡啶(1.52g,7.40mmol)溶解在甲苯(40mL)中,向其中加入2MK2CO3溶液(10mL)。将混合物用N2流脱气20分钟,并在N2气氛中加入Pd(PPh3)4(171mg,0.05mmol)。将混合物在氮气下于90℃搅拌24小时。然后将混合物冷却至室温,并用CH2Cl2萃取,并用无水Mg2SO4干燥,减压除去溶剂。固体通过柱色谱法纯化,得到R1基团为羰基的偶极有机配体(产率:650mg,66%)。
R1基团为羰基的偶极有机配体的官能团化:将R1基团为羰基的偶极有机配体(320mg,0.96mmol)和3-乙基罗丹宁(232mg,1.44mmol)和α-丙氨酸(85mg,0.95mmol)的混合物在20mlCH3COOH和20mlPhMe的混合溶液中,120℃加热反应24h。反应结束后,冷却至室温,混合物用水稀释并用CH2Cl2萃取三遍,用饱和NaHCO3溶液洗涤有机相,直到没有气体产生,用无水Mg2SO4干燥,减压除去溶剂,通过柱色谱法纯化得到红色固体产物,即官能团化的偶极有机配体(产率:280mg,61%)。
MOF的合成:将Zn(NO3)2·6H2O(59.5mg,0.2mmol),联苯二甲酸(48.4mg,0.2mmol)和偶极有机配体(95.5mg,0.2mmol)溶解在10mLDMF中。将反应混合物超声处理半小时,直到反应物完全分散溶解。然后将其转移到反应釜(或密封小瓶)中,在100℃下反应48h,冷却至室温。过滤固体产物并用DMF洗涤3遍,得到产物。
实施例7
偶极MOF的爆炸物荧光探测实验:
以实施例2制备的MOF作为代表例,通过将5mg精细研磨的活性MOF加入10mL乙腈中,超声处理1h,制得MOF悬浮液。将2mL新鲜超声处理的MOF悬浮液样品添加到石英比色皿中。然后将比色皿在328nm处激发,并在420-640nm之间测量发射光谱。测量悬浮液的初始荧光发射(I0),重复三次,取平均值,给出MOF悬浮液的初始荧光发射的基线读数。将10μL特定分析物的1mM爆炸性溶液(TzFox、4-NP、3-NP、NB、DNB等)或纯乙腈以递增方式添加到悬浮液中,直至添加200μL爆炸物(或衍生物),测量荧光发射(I)。每次测量三组数据,取平均值。将I值取平均值,然后用于计算(1-I/I0)淬灭百分比(QP)并计算检出限。
如图2所示,合成的偶极MOF可以对爆炸物TzFox进行灵敏性探测,当溶液中爆炸物浓度达到29μM时可以实现超过50%荧光猝灭,爆炸物浓度达到95μM时,猝灭效率达到90%以上。通过公式LOD=3Sb/Ksv(其中Sb为标准空白偏差,Ksv为猝灭常数)计算其检测限为0.34ppm,可以实现对溶液中的痕量爆炸物进行荧光探测(图3)。多种爆炸物荧光探测实验表明,合成的偶极MOF对多种爆炸物均存在响应,并可以实现对TzFox(Fox-7类爆炸物)的选择性探测。其他实施例制得的偶极MOF表现出与实施例2相似的性能,本发明仅以实施例2制得的偶极MOF作为代表实施例。
显然,上述实施例的列举仅仅是为清晰的说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上诉说明的基础上不仅适用于上诉吡啶端基的偶极分子,还适用于其他的偶极分子,而由此引出的金属有机框架结构的变化和修饰仍处于本发明的保护范围之内。

Claims (6)

1.基于偶极有机配体的金属有机框架材料,其特征在于,通过以下步骤合成:
将基于芴单元的偶极有机配体、辅助配体联苯二甲酸和金属源硝酸锌溶于N,N-二甲基甲酰胺中,80-140oC溶剂热反应,反应结束后,洗涤过滤,得到基于偶极有机配体的金属有机框架材料,所述的基于芴单元的偶极有机配体的结构式为
Figure DEST_PATH_IMAGE001
2.根据权利要求1所述的金属有机框架材料,其特征在于,所述的溶剂热反应的反应温度为100oC;所述的溶剂热反应的反应时间为48h;所述的金属源、辅助配体和偶极有机配体的摩尔比为1:1:0.5-1。
3.根据权利要求2所述的基于偶极有机配体的金属有机框架材料在荧光检测爆炸物中的应用。
4.根据权利要求3所述的应用,其特征在于,所述的爆炸物选自:
Figure DEST_PATH_IMAGE003
5.根据权利要求4所述的应用,其特征在于,具体方法为:
基于偶极有机配体的金属有机框架材料加入极性溶剂中制成MOF悬浮液,加入待测爆炸物溶液,检测其荧光发射光谱,根据荧光强度与爆炸物浓度的对应关系,确定爆炸物的类型和浓度。
6.根据权利要求5所述的应用,其特征在于,MOF悬浮液的浓度为0.5mg/ml;极性溶剂为水、甲醇、乙醇、乙腈、二氯甲烷、丙酮或N,N-二甲基甲酰胺。
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