CN106279219A - 用作硝基苯荧光识别传感器的双核镉配合物及其制备方法 - Google Patents
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
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Abstract
本发明涉及一种用作硝基苯荧光识别传感器的含氮二元芳香酸双核镉配合物及其制备方法。所述配合物的化学式为:[Cd2(DTP)2(BIBP)1.5],其中DTP=4′‑(4‑(3,5‑二羧基苯氧基)苯基‑4,2′:6′,4″‑三联吡啶,BIBP=4,4′‑双‑(咪唑基)联苯;它的三维骨架中具有微孔结构。在用作硝基苯荧光识别传感器时,硝基苯不会影响所述配合物荧光发射峰的位置,配合物的发射峰强度随着硝基苯浓度的增加而显著减弱(当硝基苯浓度为300ppm时,能够使配合物荧光发射峰的淬灭效率为99.8%,配合物的荧光强度从2789a.u.降低为36a.u.,发射峰强度降低为对应的空白样品峰的约77倍),其它供试有机化合物对硝基苯的荧光识别检测不会产生影响。所述配合物可以作为硝基苯荧光识别传感器,在环境监测领域具有潜在的应用前景。
Description
技术领域
本发明涉及金属配位化合物领域,特别是涉及一种用作硝基苯荧光识别传感器的含氮二元芳香酸双核镉及其制备方法。
技术背景
金属配位化合物有序的微孔结构和良好的晶化能力可有效保证其活性中心与客体分子之间的结合位点和接触面积,使其能够与电子效应和空间效应匹配的金属离子、阴离子、有机小分子等物种相互结合,从而实现其分子(离子)识别传感器、手性拆分、药物缓释、气体吸附和分离、选择性催化以及气体存储等功能。近年来,光功能导向的配位化合物已发展成为特种功能材料领域的研究热点之一[T.Devic等,Science,2005(309)2040;H.K.Chae1等,Nature,2004(427)523;S.Sanda等,Chemical Communications,2015(51)6576]。nd10过渡金属配位化合物的发光性质研究主要集中于由Cu+、Ag+、Zn2+、Cd2+等中心离子所形成的配位化合物,因中心离子具有nd10电子结构,能够有效避免d-d跃迁引起的光吸收,与这些金属离子形成的配位化合物具有独特的光学性质,可以作为刚性或柔性的主体来选择性地包裹客体分子如荧光染料、金属阳离子、阴离子或缺电子分子等物种[F.X.Coudert等,Coordination Chemistry Reviews,2016(307)211;S.Khatua等,Chemistry of Materials,2015(27)5349;H.Wang等,Angewandte Chemie InternationalEdition,2015(54)5966]。
硝基苯是医药、农药、染料、橡胶、香料等工业产生的污染物,对环境和生物具有严重的危害作用。研究表明,过渡金属配位化合物对硝基苯类衍生物以及硝基取代的爆炸物具有荧光识别功能,对该方向的系统研究在生命科学、环境科学等领域具有潜在的理论意义和应用前景[Z.Hu等,Chemical Society Reviews,2014(43)5815;A.Lan等,AngewandteChemie International Edition,2009(48)2334;S.Pramanik等,Journal of theAmerican Chemical Society,2011(133)4153;S.N.Sanjog,CrystEngComm,2016(18)2994]。本发明所涉及的含氮二元芳香酸双核镉配合物,300ppm的硝基苯可使其荧光淬灭效率达到99.8%,具备操作简便快捷、对环境友好、灵敏性高以及选择性强的特点,该种双核镉配合物作为硝基苯荧光识别传感器尚未见文献报道。
发明内容
本发明提供一种用作硝基苯荧光识别传感器的含氮二元芳香酸双核镉配合物,及其制备方法。本发明的目的通过如下技术方案来实现:
一种用作硝基苯荧光识别传感器的含氮二元芳香酸双核镉配合物,其特征在于,所述配合物化学式为[Cd2(DTP)2(BIBP)1.5],其中DTP为4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶,BIBP为4,4′-双-(咪唑基)联苯;
所述配合物的主要红外吸收峰为(单位:cm-1):3417(br),1607(s),1556(s),1513(s),1453(w),1396(m),1364(m),1244(s),1128(w),1177(w),1109(w),1065(m),1014(w),963(w),827(s),779(w),778(w),729(m),625w),638(w),514(m)。
上述双核镉配合物的晶胞参数为:其晶体属于三斜晶系,空间群为P-1,晶胞参数为:α=85.5670(10)°,β=76.2310(10)°,γ=85.8780(10)°,晶胞体积为中心离子Cd1、Cd2均为畸变的配位八面体几何构型;Cd1离子与来自两个DTP配体的四个羧基氧原子和隶属于两个BIBP的两个氮原子配位,Cd2离子与两个DTP配体的三个羧基氧原子以及三个BIBP的三个氮原子配位。
进一步地,本申请保护一种硝基苯荧光识别传感器,其特征在于,所述硝基苯荧光识别传感器具有由上述含氮二元芳香酸双核镉配合物所形成的具有微孔的三维空间网状结构。
进一步地,本发明涉及上述含氮二元芳香酸双核镉配合物的制备方法,其特征在于,所述制备方法包括如下步骤:
1)将4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶(DTP)、4,4′-双-(咪唑基)联苯(BIBP)和高氯酸镉[Cd(ClO4)2·6H2O]溶于N,N-二甲基甲酰胺(DMF)与蒸馏水的混合溶剂中,在室温下搅拌30分钟;所述的4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶、4,4′-双-(咪唑基)联苯、高氯酸镉和混合溶剂的重量份为:30~40∶20~25∶30~35∶7980~8010;混合溶剂中N,N-二甲基甲酰胺与蒸馏水的体积份为:2~6∶1~3;
2)将上述混合液转移至25mL水热反应釜的聚四氟乙烯内胆中,在150℃和pH=5.0~6.5的条件下反应72小时;
3)自然冷却至室温,将所得产物过滤并用蒸馏水洗涤两次(1mL/次),得到浅黄色的目标产物,所述浅黄色的目标产物为块状晶体。
优选地,步骤1)中,4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶、4,4′-双-(咪唑基)联苯、高氯酸镉和混合溶剂的重量份为:30~40:20~25:30~35∶7980~8010;混合溶剂中N,N-二甲基甲酰胺与蒸馏水的体积份为:2~6∶1~3。更优选为32∶24∶32∶8000,混合溶剂中N,N-二甲基甲酰胺与蒸馏水的体积比为:3∶2。
进一步地,本发明提供将上述含氮二元芳香酸双核镉配合物用作硝基苯荧光识别传感器的应用,以用于监测环境中的硝基苯。
原理说明:本发明选用4′-(4-(3,5-二羧基苯氧基)苯基-4,2′∶6′,4″-三联吡啶配体,以4,4′-双-(咪唑基)联苯为辅助配体,与高氯酸镉构筑了具有微孔结构的三维双核镉配合物。在用作硝基苯荧光识别传感器时,硝基苯不会影响所述含氮二元芳香酸双核镉配合物荧光发射峰的位置,配合物的发射峰的强度随着硝基苯浓度的增加而显著减弱(当硝基苯浓度为300ppm时,能够使配合物荧光发射峰的淬灭效率达到99.8%,配合物的荧光强度从2789a.u.降低为36a.u.,峰强度降低为对应的空白样品峰的约77倍);而分别添加其它供试有机化合物则其荧光强度变化不明显,当硝基苯分别与供试有机化合物共存于镉配合物的溶液中时,配合物荧光发射峰的淬灭效率依然可以达到约99.8%,说明其它供试有机化合物对硝基苯的荧光识别检测不会产生影响。所述配合物可以作为硝基苯的荧光识别传感器,在环境监测领域具有潜在的应用前景。
由nd10过渡金属构筑的配位化合物可被看作大的分子体系,其共价键和导带类似于分子轨道,通常情况下,配位化合物的导带处于能量较高的轨道,该能量高于待检测分子的最低空轨道,据此,这种能量差成为电子和能量向缺电子物种转移的驱动力,从而导致金属配位化合物的荧光淬灭,因而,配位化合物对具有特定电子效应的物种表现出高度的识别功能;配合物的配体中羧基数目的增多更有利于电子和能量的转移,上述实验事实和荧光淬灭机理得到了量子化学计算结果的佐证[S.Pramanik等,Journal of the AmericanChemical Society,2011(133)4153;阳庆元等,化工学报,2009(60)805]。对于nd10过渡金属配位化合物的发光原理以及其荧光淬灭机理研究有助于该类化合物的功能导向、分子设计和定向合成。
有报道表明金属配合物能够作为检测阴阳离子、溶剂分子、生物小分子和爆炸物等的荧光探针,这些物种能够导致配合物荧光强度增强或淬灭,荧光强度的改变与待测物种的浓度呈现相关性,据此,可以定性确定或定量标定体系中该物种的存在和浓度。本发明涉及的微孔三维双核镉配合物对于硝基苯具有良好的选择性识别作用,镉配合物荧光发射峰位置不变,发射峰强度随着硝基苯浓度的增加而明显降低,当硝基苯浓度为300ppm时,使配合物荧光发射峰的淬灭效率达到99.8%,配合物的荧光强度从2789a.u.降低为36a.u.,峰强度降低为对应的空白样品峰的约77倍。硝基苯是医药、农药、染料、橡胶、香料等工业产生的环境污染物,通过水体、食物进入生物体后会产生严重的毒害作用。本发明可望应用于环境中硝基苯的定性和定量检测。
附图说明:
图1本发明双核镉配合物的晶体结构图。
图2本发明双核镉配合物的三维孔洞结构图。
图3不同浓度的硝基苯对双核镉配合物的荧光淬灭效率对比图。
图4本发明双核镉配合物在1,4-二氧六环、甲苯、二甲基亚砜、乙腈、N,N-二甲基甲酰胺、苯或甲醇存在时在346nm(λex=305nm)处的荧光强度。
具体实施方式
为了更好的理解本发明,下面结合实施实例进一步阐述本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
实施例1 配合物的合成:
将0.0367g(0.075mmol)4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶、0.0215g(0.075mmol)4,4′-双-(咪唑基)联苯、0.0322g(0.075mmol)Cd(ClO4)2·6H2O按比例为1∶1∶1(物质的量比)溶于8mL N,N-二甲基甲酰胺与蒸馏水的混合溶剂中,在室温下调节混合溶液的pH值为5.7,搅拌30分钟,转移至25mL水热反应釜的聚四氟乙烯内胆中,在150℃温度条件下反应72小时,自然冷却至室温,所得产物用蒸馏水洗涤两次(1mL/次),得到浅黄色的块状晶体,基于Cd(ClO4)2·6H2O计算的产率为78.33%。
实施例2 配合物的结构表征:
晶体结构采用Bruker Smart CCD X-射线单晶衍射仪,在296(2)K下,挑选尺寸为0.34×0.26×0.22mm3的块状晶体,使用经过石墨单色化的MoKα射线(λ=0.07107nm)为入射辐射光源,以ω/2θ扫描方式收集衍射点,晶胞参数经最小二乘法精修,用SADABS程序对收集到的数据进行吸收校正。用直接法解出配合物的结构,运用全矩阵最小二乘法对非氢原子坐标和各向异性温度因子进行精修,用SHELXTL程序完成全部计算。详细的晶体学参数列于表1。双核镉配合物[Cd2(DTP)2(BIBP)1.5]的晶体结构及三维孔洞结构如图1和图2所示。
表1双核镉配合物的晶体学数据
实施例3 配合物的荧光性质:
采用F-7000FL型荧光光谱仪,在室温下测定了双核镉配合物在N,N-二甲基乙酰胺(DMA)溶液中的荧光光谱,激发光波长为305nm,发射峰位于346nm处。与双核镉配合物空白样品(不添加任何待检测的有机化合物)相比,当硝基苯(Nitrobenzene,NB)的浓度在0ppm~600ppm之间变化时,配合物的发射峰位置没有发生位移,但其发射峰的强度随着硝基苯的浓度增加而明显减弱。当硝基苯浓度为300ppm时,能够使配合物荧光发射峰的淬灭效率达到99.8%,配合物的荧光强度从2789a.u.降低为36a.u.,峰强度降低为对应的空白样品峰的约77倍,如图3所示;与上述实验相同,向双核镉配合物的N,N-二甲基乙酰胺(DMA)溶液中分别添加1000ppm的1,4-二氧六环(1,4-dioxane)、甲苯(toluene)、二甲基亚砜(dimethyl sulfoxide,DMSO)、乙腈(acetonitrile,CH3CN)、N,N-二甲基甲酰胺(N,N-dimethylformamide,DMF)、苯(benzene)或甲醇(methanol)后,混合体系的荧光强度与配合物空白样品相比,发射峰位置没有发生明显位移,且荧光强度变化较小,分别向上述混合溶液中添加浓度为300ppm的硝基苯时,则配合物的荧光强度几乎完全淬灭,如图4所示,表明双核镉配合物对硝基苯具有较强的荧光选择性,并且不会受到上述化合物的干扰,该配合物可望成为痕量硝基苯的荧光识别传感器。
图3本发明的双核镉配合物在不同浓度的硝基苯存在时的荧光光谱图(λex=305nm,λem=346nm):曲线I:配合物空白样品的发射光谱图(不添加任何待检测的有机化合物);曲线II:硝基苯浓度为300ppm时,配合物的发射光谱图。
图4本发明的配合物在346nm(λex=305nm)处添加1000ppm的有机化合物的荧光发射峰强度。各柱形图所指如下:I:1,4-二氧六环(1,4-dioxane),II:甲苯(toluene),III:二甲基亚砜(DMSO),IV:乙腈(CH3CN),V:N,N-二甲基甲酰胺(DMF),VI:苯(benzene),VII:甲醇(methanol),上述各柱形图表示在配合物的N,N-二甲基乙酰胺(DMA)溶液中分别添加1000ppm的上述各种有机化合物的荧光强度;VIII:向上述溶液中添加300ppm硝基苯后各种溶液的荧光强度。
实施例4 六种镉配合物对硝基苯荧光选择性的比较:
采用相同配体4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶(DTP)合成了配合物[Cd(DTP)(H2O)],采用与实施例3的相同的实验条件,与本发明的双核镉配合物相比较,前者对硝基苯几乎没有荧光选择性;文献报道的以镉为中心离子的多元羧酸配合物也对硝基苯具有不同效率的识别作用,与本发明的镉配合物对硝基苯的识别效率相关数据列于下表,结构分析表明本发明所述的镉配合物具有结构简单、合成条件温和等特点。
六种镉配合物对硝基苯的荧光淬灭效率
注1:“-”表示硝基苯对配合物荧光强度不产生影响。
注2:DTP=4′-(4-(3,5-dicarboxylphenoxy)phenyl)-4,2′:6′,4″-terpyridine,BIBP=4′4-bis(imidazolyl)biphenyl;
L1=1,1’-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylic acid),NTB=4,4’,4”-nitrilotrisbenzoic acid,DMA=N,N-dimethylacetamide;
L2=2,4,6-tri[1-(3-carboxylphenoxy)-ylmethyl]mesitylene,DMF=N,N-dimethylformamide;
TPTZ={4-[4-(1H-1,2,4-triazol-1-yl)phenyl]phenyl}-1H-1,2,4-triazole,IPA=isophthalic acid.
本发明的用作硝基苯荧光识别传感器的二元芳香酸双核镉配合物及其制备方法已经通过具体的实例进行了描述,本领域技术人员可借鉴本发明内容,适当改变原料、工艺条件等环节来实现相应的其它目的,其相关改变都没有脱离本发明的内容,所有类似的替换和改动对于本领域技术人员来说是显而易见的,都被视为包括在本发明的范围之内。
Claims (7)
1.一种用作硝基苯荧光识别传感器的含氮二元芳香酸双核镉配合物,其特征在于,所述配合物化学式为[Cd2(DTP)2(BIBP)1.5],其中DTP为4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶,BIBP为4,4′-双-(咪唑基)联苯;
所述配合物的主要红外吸收峰为(单位:cm-1):3417(br),1607(s),1556(s),1513(s),1453(w),1396(m),1364(m),1244(s),1128(w),1177(w),1109(w),1065(m),1014(w),963(w),827(s),779(w),778(w),729(m),625w),638(w),514(m)。
2.根据权利要求1所述的含氮二元芳香酸双核镉配合物,其特征在于,其晶体属于三斜晶系,空间群为P-1,晶胞参数为: α=85.5670(10)°,β=76.2310(10)°,γ=85.8780(10)°,晶胞体积为中心离子Cd1、Cd2均为畸变的配位八面体几何构型;Cd1离子与来自两个DTP配体的四个羧基氧原子和隶属于两个BIBP的两个氮原子配位,Cd2离子与两个DTP配体的三个羧基氧原子以及三个BIBP的三个氮原子配位。
3.根据权利要求1或2所述的含氮二元芳香酸双核镉配合物的制备方法,其特征在于,所述制备方法包括如下步骤:
1)将4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶、4,4′-双-(咪唑基)联苯和高氯酸镉溶于N,N-二甲基甲酰胺与蒸馏水的混合溶剂中,在室温下搅拌30分钟,所述高氯酸镉为Cd(ClO4)2·6H2O;所述的4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶、4,4′-双-(咪唑基)联苯、高氯酸镉和混合溶剂的重量份为:30~40∶20~25∶30~35∶7980~8010;混合溶剂中N,N-二甲基甲酰胺与蒸馏水的体积份为:2~6∶1~3;
2)将上述混合液转移至25mL水热反应釜的聚四氟乙烯内胆中,在150℃和pH=5.0~6.5的条件下反应72小时;
3)自然冷却至室温,将所得产物过滤并用蒸馏水洗涤两次(1mL/次),得到浅黄色的目标产物,所述浅黄色的目标产物为块状晶体。
4.根据权利要求3所述的制备方法,其特征在于,步骤1)中,4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶、4,4′-双-(咪唑基)联苯、高氯酸镉和混合溶剂的重量份为:30~40∶20~25∶30~35∶7980~8010;混合溶剂中N,N-二甲基甲酰胺与蒸馏水的体积份为:2~6∶1~3。
5.根据权利要求3所述的制备方法,其特征在于,步骤1)中,4′-(4-(3,5-二羧基苯氧基)苯基-4,2′:6′,4″-三联吡啶、4,4′-双-(咪唑基)联苯、高氯酸镉和混合溶剂的重量份为:32∶24∶32∶8000,混合溶剂中N,N-二甲基甲酰胺与蒸馏水的体积比为:3∶2。
6.根据权利要求1或2所述的含氮二元芳香酸双核镉配合物用作硝基苯荧光识别传感器的应用,以用于监测环境中的硝基苯。
7.一种硝基苯荧光识别传感器,其特征在于,所述硝基苯荧光识别传感器具有由权利要求1或2所述的含氮二元芳香酸双核镉配合物所形成的具有微孔的三维空间网状结构。
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CN111704627A (zh) * | 2020-05-26 | 2020-09-25 | 信阳师范学院 | 2,3,3′,4′-联苯四羧酸和4,4′-联吡啶的镉配合物及其制备方法及其应用 |
CN111704627B (zh) * | 2020-05-26 | 2022-06-28 | 信阳师范学院 | 2,3,3′,4′-联苯四羧酸和4,4′-联吡啶的镉配合物及其制备方法及其应用 |
CN116396492A (zh) * | 2023-04-12 | 2023-07-07 | 重庆师范大学 | 含不对称结构单元镉基杂化材料及其制法与在制备补光器件中的应用 |
CN116396492B (zh) * | 2023-04-12 | 2024-05-28 | 重庆师范大学 | 含不对称结构单元镉基杂化材料及其制法与在制备补光器件中的应用 |
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