CN106397781A - 具有中心离子调节荧光发射性质的配位聚合物的制备方法 - Google Patents
具有中心离子调节荧光发射性质的配位聚合物的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 8
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 8
- 150000002500 ions Chemical class 0.000 title claims 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 2
- -1 metals salt Chemical class 0.000 claims 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L Cadmium chloride Inorganic materials Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 239000011565 manganese chloride Substances 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 13
- 239000003446 ligand Substances 0.000 abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Abstract
本发明涉及一种具有中心离子调节荧光发射性质的配位聚合物的制备方法，包括下述步骤：多种金属盐和氨基三亚甲基膦酸按摩尔比例为1‑1.5溶于去离子水中；使用0.1 M KOH溶液调节pH为3‑4，然后机械搅拌3‑5 h，将混合溶液封装在反应釜中，150‑180 °C加热5‑7 d，最后，冷却至室温，有块状晶体析出。本发明是利用含膦酸基配体，与五种廉价的金属盐形成结构相同的配合物，通过金属离子的变化，达到调控配合物的荧光性质的目的，实现荧光发射性质的可控性。本发明中的配合物热稳定性良好，可以达到200 ℃左右仅失去配位水分子，而配合物的结构不被破坏。同时，通过改变金属离子调控配合物的荧光性质。
Description
技术领域
本发明涉及一种配位聚合物，尤其涉及一种具有中心离子调节荧光发射性质的配位聚合物的制备方法。
背景技术
现有研究配合物的荧光发射性质主要集中在增加配合物的共轭体系来改变配合物的电荷转移，从而改变荧光性质。研究的重点只是单个配合物的荧光性质。其荧光发射机理包括，金属-配体电荷转移，配体间的电荷转移等。其研究时选择的金属离子多以稀土元素为主。
现有的荧光材料种类繁多，包括（1）含氮杂环和芳香环等共轭有机化合物，该类化合物的合成步骤较多，合成费用不菲；（2）含共轭芳香环的配合物。但是，对于这些荧光材料的荧光发射性质的影响因素以及调控因素研究的很少。
发明内容
本发明的目的是建立基于配合物荧光性质的一种通过金属离子的不同来调节配合物的荧
光发射性质。拓展调节配合物荧光发射性质的影响因素。
本发明的技术方案如下：
配合物的制备：多种金属盐和氨基三亚甲基膦酸按摩尔比例为1:1-1.5溶于去离子水中；使用0.1 M KOH溶液调节pH为3-4，然后机械搅拌3-5 h，将混合溶液封装在反应釜中，150-180 °C加热5-7 d，最后，冷却至室温，有块状晶体析出。
配合物的制备：多种金属盐和氨基三亚甲基膦酸按摩尔比例为1:1溶于去离子水中；使用0.1 M KOH溶液调节pH为3-4，然后机械搅拌3 h，将混合溶液封装在18 mL反应釜中，150 °C加热7 d，最后，冷却至室温，有块状晶体析出。
所述的金属盐包括MgCl2、MnCl2、CoCl2、ZnCl2和CdCl2五种。
所述的金属盐与去离子水的用量比例为，1mmol的金属盐溶于10ml去离子水中。
本发明与现有技术相比所具有的优点及效果：
本发明是利用含膦酸基配体，与五种廉价的金属盐形成结构相同的配合物，通过金属离子
的变化，达到调控配合物的荧光性质的目的，实现荧光发射性质的可控性。本发明中的配合物热稳定性良好，可以达到200 ℃左右仅失去配位水分子，而配合物的结构不被破坏。同时，通过改变金属离子调控配合物的荧光性质。表征结果表明，该方法制备得到的配合物可以通过金属离子的改变进而调节配合物的荧光发射性质，目的是通过简单地手段来调节配合物的荧光性质。
附图说明
图1为配合物的分子结构示意图。
图2为配合物1-5的热重曲线示意图。
图3为室温下，配合物1-5与配体的固态荧光发射谱图（L: 配体）。
具体实施方式
实施例1
配合物的制备：金属盐(MgCl2 (1), MnCl2 (2), CoCl2 (3), ZnCl2 (4)和CdCl2 (5))和氨基三亚
甲基膦酸按摩尔比例为1:1溶于去离子水中，金属盐与去离子水的用量比例为，1mmol的金属盐溶于10ml去离子水中；使用0.1 M KOH溶液调节pH为3-4，然后机械搅拌3 h，将混合溶液封装在18 mL反应釜中，150 °C加热7 d，最后，冷却至室温，有块状晶体析出。产率分别为73% (1)，63% (2)，83% (3)，81% (4)和70% (5)。
由附图可知，配体的荧光发射峰在398 nm，发射带为320-650 nm。配合物1-5均显示出两
个较强的发射峰，分别为448/472，417/441，413/435，418/434和417/435 nm。荧光发射带分别为414-650 (1)，383-650 nm (2-5)。与配体相比，配合物1-5的荧光发射峰均发生了红移。分别红移了74，43，37，36和37 nm。红移幅度是 1 > 2 > 3, 和4 ≈ 5。与配体相比，配合物1-5的荧光发射带缩短了94，63，63 (1-3)和63 nm (4-5)，缩短幅度是1 > 2 = 3，4= 5。对于荧光发射强度，配合物1-3有所减弱，配合物4和5有所增强。
与其他荧光材料相比，本发明的配合物材料具有以下几个突出的特点：(1)具有良好的热
稳定性，可以200 ℃左右仅失去溶剂分子，配合物结构没有被破坏；(2)其配合物的荧光发射性质可以通过改变中心金属离子加以调控；(3)配合物1-5的荧光发射效果改变明显，包括荧光发射带，强度以及发射波长；(4)该配合物的合成方法简单，合成步骤少，合成成本便宜，所用原料廉价。
实施例2
配合物的制备：金属盐(MgCl2 (1), MnCl2 (2), CoCl2 (3), ZnCl2 (4) and CdCl2(5))和氨基三亚甲基膦酸按摩尔比例为1:1.5溶于去离子水中；使用0.1 M KOH溶液调节pH为3-4，然后机械搅拌5 h，将混合溶液封装在反应釜中，180 °C加热5 d，最后，冷却至室温，有块状晶体析出。
实施例3
配合物的制备：金属盐(MgCl2 (1), MnCl2 (2), CoCl2 (3), ZnCl2 (4)和CdCl2 (5))和氨基三亚甲基膦酸按摩尔比例为1:1.2溶于去离子水中；使用0.1 M KOH溶液调节pH为3-4，然后机械搅拌4 h，将混合溶液封装在反应釜中，160 °C加热6 d，最后，冷却至室温，有块状晶体析出。
Claims (4)
1.一种具有中心离子调节荧光发射性质的配位聚合物的制备方法，其特征在于包括下述步骤：多种金属盐和氨基三亚甲基膦酸按摩尔比例为1:1-1.5溶于去离子水中；使用0.1M KOH溶液调节pH为3-4，然后机械搅拌3-5 h，将混合溶液封装在反应釜中，150-180 °C加热5-7 d，最后，冷却至室温，有块状晶体析出。
2.根据权利要求1所述的具有中心离子调节荧光发射性质的配位聚合物的制备方法，其特征在于优选参数为，多种金属盐和氨基三亚甲基膦酸按摩尔比例为1:1溶于去离子水中；使用0.1 M KOH溶液调节pH为3-4，然后机械搅拌3 h，将混合溶液封装在18 mL反应釜中，150 °C加热7 d，最后，冷却至室温，有块状晶体析出。
3.根据权利要求1或2所述的具有中心离子调节荧光发射性质的配位聚合物的制备方法，其特征在于所述的金属盐包括MgCl2、MnCl2、CoCl2、ZnCl2和CdCl2五种。
4.根据权利要求1或2所述的具有中心离子调节荧光发射性质的配位聚合物的制备方法，其特征在于所述的金属盐与去离子水的用量比例为，1mmol的金属盐溶于10ml去离子水中。
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| CN106543453A (zh) * | 2016-10-26 | 2017-03-29 | 辽宁石油化工大学 | 一种链状超低温磁学配位聚合物材料的制备方法 |
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| CN105101948A (zh) * | 2013-04-18 | 2015-11-25 | 宝洁公司 | 包含吡啶硫酮锌和金属-膦酸盐络合物的个人护理组合物 |
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| CN106543453A (zh) * | 2016-10-26 | 2017-03-29 | 辽宁石油化工大学 | 一种链状超低温磁学配位聚合物材料的制备方法 |
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Application publication date: 20170215 |