CN106589395A - 化学式为[CdC16H10N2O4S]n的金属有机框架化合物及其制备方法和应用 - Google Patents
化学式为[CdC16H10N2O4S]n的金属有机框架化合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种化学式为[CdC16H10N2O4S]n的金属有机框架化合物及其制备方法和应用。以Cd(NO3)2·9H2O、噻吩‑2,5‑二甲酸(2,5‑tdc)、4,4’‑联吡啶(4,4’‑pydc)和氢氧化钠为原料,利用水热法,在170℃下进行反应72小时,然后进行程序降温至100℃,保温10 h,再缓慢冷却至室温,即制得化学式为[CdC16H10N2O4S]n的金属有机框架化合物,该化合物属于三斜晶系晶体,Cmca空间群,a=1.17174 nm,b=1.54697 nm,c=1.93354 nm,α=90°,β=90°,γ=90°,V=3.50482 nm3,面心晶胞F(000)=1728,Goof=1.043,Z=8,该金属有机框架化合物具有较强的荧光性质,能够作为荧光探针应用于荧光分析领域。本发明制备方法操作简单,绿色环保,且所制得的金属有机框架化合物具有较强的荧光性质,应用前景广阔。
Description
技术领域
本发明属于金属有机框架化合物技术领域,特别涉及一种化学式为[CdC16H10N2O4S]n的金属有机框架化合物及其制备方法和应用。
背景技术
金属有机框架化合物(MOFs)从结构上看,是一类由有机配体和无机金属单元通过共价键、氢键等形成的从一维到三维的无限网状结构。在MOFs材料中,一般以金属离子为连接点,以有机配位体为支撑,以此来构筑3D空间网络结构。从其结构上看,在这种配合物结构框架中,配体小分子与中心离子之间并不是简单物理堆积,而是通过一定的化学作用连接在一起,如化学键、范德华力、离子键及氢键作用等。它们的排列具有方向性,引入有特殊性能和结构的配体可以合成结构和功能可预测的且排列可控制的MOFs。
关于MOFs的设计与合成的研究工作相对较多,而该领域也得到了充分的发展,从最初的探索MOFs的合成规律,到开展晶体结构的设计研究,并有目的的进行合成功能性MOFs材料。在设计合成的过程中,金属离子和有机配体的选择是至关重要的。不同金属离子的电子结构和配位性质直接影响了MOFs的晶体结构和性质。在有机配体的选择方面,也经历了长足的发展,从氮杂环、含硫杂环等有机配体到羧酸、磺酸、磷酸配体均有涉及。在MOFs的构筑中,接酸配体是一类非常重要的有机配体,酸类有机配体种类繁多,存在多个配位点且配位方式也多种多样。相对脂肪类羧酸配体而言,芳香羧酸配体更具刚性,易与金属离子形成具有孔洞结构的配位聚合物,易于得到有趣的拓扑网络结构,并且具有很好的稳定性。人们可以计划性地选择金属和配体,通过控制影响MOFs构筑过程中的各种微妙因素,设计合成具有特定结构和潜在功能的配位聚合物,这对晶体工程的研究具有非常重要的意义。
本申请提供了一种以噻吩-2,5-二甲酸、4,4,-联吡啶、无机金属盐为原料,水热法合成化学式为[CdC16H10N2O4S]n金属有机框架化合物(MOFs)的方法,并提出了可利用其较强的荧光性质用作荧光探针使用。
发明内容
本发明的目的是提供一种化学式为[CdC16H10N2O4S]n的金属有机框架化合物及其制备方法和应用。
本发明的化学式为[CdC16H10N2O4S]n的金属有机框架化合物属于三斜晶系晶体,其晶体学参数见表1,部分键长和键角见表2。
表1化学式为[CdC16H10N2O4S]n的金属有机框架化合物的晶体学参数
表2化学式为[CdC16H10N2O4S]n的金属有机框架化合物的部分键长(nm)和键角(°)
A)-x,-y+1/2,z+1/2;B)x,y-1/2,-z+1/2;C)x,y+1/2,-z+1/2;D)-x,-y+1/2,z-1/2;E)-x,y,z;F)-x+1,y,z。
制备上述化学式为[CdC16H10N2O4S]n的金属有机框架化合物的具体步骤为:
(1)将10mL含有0.5mmol(0.281g)Cd(NO3)2·9H2O、0.5mmol(0.0861g)噻吩-2,5-二甲酸(2,5-tdc)、0.5mmol(0.0837g)4,4’-联吡啶(4,4’-pydc)和1mmol(0.0398g)氢氧化钠的蒸馏水溶液,室温下磁力搅拌1h,制得混合溶液。
(2)将步骤(1)制得的混合溶液转移到到25mL带有聚四氟乙烯衬底的水热反应釜中,将水热反应釜放入烘箱中加热到170℃晶化72h,然后进行程序降温至100℃,保温10h,关掉烘箱让其在自然状态下冷却至室温,取出水热反应釜,有粉色针状晶体生成,过滤,自然晾干后收集样品,即制得化学式为[CdC16H10N2O4S]n的金属有机框架化合物。
本发明的化学式为[CdC16H10N2O4S]n的金属有机框架化合物具有较强的荧光性质,能够作为荧光探针应用于荧光分析领域。
本发明制备方法操作简单,绿色环保,且所制得的化学式为[CdC16H10N2O4S]n的金属有机框架化合物具有较强的荧光性质,应用前景广阔。
附图说明
图1为本发明化学式为[CdC16H10N2O4S]n的金属有机框架化合物的晶体结构图。
图2为本发明化学式为[CdC16H10N2O4S]n的金属有机框架化合物的配位多面体图。
图3为本发明化学式为[CdC16H10N2O4S]n的金属有机框架化合物的晶体三维堆积图(c方向)。
图4为本发明化学式为[CdC16H10N2O4S]n的金属有机框架化合物的DMF溶液荧光光谱图。
具体实施方式
实施例:
(1)将10mL含有0.5mmol(0.281g)Cd(NO3)2·9H2O、0.5mmol(0.0861g)噻吩-2,5-二甲酸(2,5-tdc)、0.5mmol(0.0837g)4,4’-联吡啶(4,4’-pydc)和1mmol(0.0398g)氢氧化钠的蒸馏水溶液,室温下磁力搅拌1h,制得混合溶液。
(2)将步骤(1)制得的混合溶液转移到到25mL带有聚四氟乙烯衬底的水热反应釜中,将水热反应釜放入烘箱中加热到170℃晶化72h,然后进行程序降温至100℃,保温10h,关掉烘箱让其在自然状态下冷却至室温,取出水热反应釜,有粉色针状晶体生成,过滤,自然晾干后收集样品,即制得化学式为[CdC16H10N2O4S]n的金属有机框架化合物。其晶体学参数见表1,部分键长和键角见表2,晶体结构图见图1,配位多面体图见图2,c方向堆积图见图3。
本实施例制得的化学式为[CdC16H10N2O4S]n的金属有机框架化合物的荧光发射(Em)和激发(Ex)光谱如图4所示,该化合物最大发射波长,λEm=324nm,较配体H4BETA发生了蓝移,可能是因为配体与金属离子键合后,其扭转的构型限制了弛豫跃迁。说明该化合物具有荧光性质,能够作为荧光探针应用于荧光分析领域。
Claims (3)
1.一种化学式为[CdC16H10N2O4S]n的金属有机框架化合物,其特征在于该金属有机框架化合物属于三斜晶系晶体,其晶体学参数见表1,部分键长和键角见表2:
表1化学式为[CdC16H10N2O4S]n的金属有机框架化合物的晶体学参数
表2化学式为[CdC16H10N2O4S]n的金属有机框架化合物的部分键长(nm)和键角(°)
A)-x,-y+1/2,z+1/2;B)x,y-1/2,-z+1/2;C)x,y+1/2,-z+1/2;D)-x,-y+1/2,z-1/2;E)-x,y,z;F)-x+1,y,z。
2.一种如权利要求1所述的化学式为[CdC16H10N2O4S]n的金属有机框架化合物的制备方法,其特征在于具体步骤为:
(1)将10mL含有0.5mmol(0.281g)Cd(NO3)2·9H2O、0.5mmol(0.0861g)噻吩-2,5-二甲酸(2,5-tdc)、0.5mmol(0.0837g)4,4’-联吡啶(4,4’-pydc)和1mmol(0.0398g)氢氧化钠的蒸馏水溶液,室温下磁力搅拌1h,制得混合溶液;
(2)将步骤(1)制得的混合溶液转移到到25mL带有聚四氟乙烯衬底的水热反应釜中,将水热反应釜放入烘箱中加热到170℃晶化72h,然后进行程序降温至100℃,保温10h,关掉烘箱让其在自然状态下冷却至室温,取出水热反应釜,有粉色针状晶体生成,过滤,自然晾干后收集样品,即制得化学式为[CdC16H10N2O4S]n的金属有机框架化合物。
3.根据权利要求2所述的方法制得的化学式为[CdC16H10N2O4S]n的金属有机框架化合物的应用,其特征在于该化学式为[CdC16H10N2O4S]n的金属有机框架化合物作为荧光探针应用于荧光分析领域。
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CN107652439A (zh) * | 2017-09-22 | 2018-02-02 | 宁波大学 | 一种镉金属有机框架材料及其制备方法和应用 |
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CN110590817A (zh) * | 2019-09-19 | 2019-12-20 | 桂林理工大学 | 3,4-乙撑二氧基噻吩-2,5-二羧酸镉配合物及其制备方法 |
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CN107794036A (zh) * | 2017-09-25 | 2018-03-13 | 桂林理工大学 | 基于噻吩‑2,5‑二羧酸和4,4′‑联吡啶构筑的金属有机框架化合物的合成及应用 |
CN110040783A (zh) * | 2019-05-20 | 2019-07-23 | 新乡医学院 | 四氧化三锰纳米材料、其制备方法及应用 |
CN110040783B (zh) * | 2019-05-20 | 2021-09-10 | 新乡医学院 | 四氧化三锰纳米材料、其制备方法及应用 |
CN110551293A (zh) * | 2019-09-19 | 2019-12-10 | 桂林理工大学 | 3,4-乙撑二氧基噻吩-2,5-二羧酸锌配合物及其制备方法 |
CN110590817A (zh) * | 2019-09-19 | 2019-12-20 | 桂林理工大学 | 3,4-乙撑二氧基噻吩-2,5-二羧酸镉配合物及其制备方法 |
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