CN106167501A - 一种对苯二甲酸和2,4,5‑三(4‑吡啶基)‑1h‑咪唑混配的铜配合物、其制备方法及应用 - Google Patents
一种对苯二甲酸和2,4,5‑三(4‑吡啶基)‑1h‑咪唑混配的铜配合物、其制备方法及应用 Download PDFInfo
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- 150000004699 copper complex Chemical class 0.000 title claims abstract description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 239000003446 ligand Substances 0.000 claims abstract description 8
- -1 p-phthalic acid anion Chemical class 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- 230000009514 concussion Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
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- 150000002460 imidazoles Chemical class 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
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- YJOAHXHOXMAHOG-UHFFFAOYSA-N 4-(2,4-dipyridin-4-yl-1h-imidazol-5-yl)pyridine Chemical compound C1=NC=CC(C=2NC(=C(N=2)C=2C=CN=CC=2)C=2C=CN=CC=2)=C1 YJOAHXHOXMAHOG-UHFFFAOYSA-N 0.000 description 2
- VAYOSLLFUXYJDT-RDTXWAMCSA-N Lysergic acid diethylamide Chemical compound C1=CC(C=2[C@H](N(C)C[C@@H](C=2)C(=O)N(CC)CC)C2)=C3C2=CNC3=C1 VAYOSLLFUXYJDT-RDTXWAMCSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011896 sensitive detection Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
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Abstract
本发明的目的在于提供一种对苯二甲酸和2,4,5‑三(4‑吡啶基)‑1H‑咪唑混配的铜配合物、其制备方法及应用，所述铜配合物的分子式为[Cu2(L)2(Htpim)2(H2O)2]n，其中L为对苯二甲酸阴离子配体，Htpim 为2,4,5‑三(4‑吡啶基)‑1H‑咪唑配体。该铜配合物具有二维44拓扑结构，常温下具有稳定的光学性能。
Description
技术领域
本发明属于过渡金属配合物技术领域，具体涉及一种对苯二甲酸和2,4,5-三(4-吡啶基)-1H-咪唑混配的铜配合物、其制备方法及应用。
背景技术
由于d10金属可以与配体之间发生金属到配体电荷迁移(MLCT)，或配体到金属电荷迁移(LMCT)，或者改变配体的荧光效率，人们对d10闭壳层过渡金属配合物的发光性质研究越来越多。最近也有Zn、Ag等配合物的光学性质的报道 [Hickey, J. L.; James, J. L.;Henderson, C. A.; Price, K. A.; Mot, A. I.; Buncic, G.; Crouch, P. J.; White,J. M.; White, A. R.; Smith, T. A.; Donnelly, P. S. Inorg. Chem. 2015, 54,9556;Mohapatra, B.; Verma, S. Cryst. Growth Des. 2016, doi: 10.1021/acs.cgd.5b01257]。由于Cu(II)的配合物具有广泛的用途[Bouwman, E.; Driessen, W.L.; Reedijk, J. Coord. Chem. Rev.1990, 104, 143; Solomon, E. I.; Sarangi, R.;Woertink, J. S.; Augustine, A. J.; Yoon, J.; Ghosh, S. Acc. Chem. Res.2007,40, 581]。但是Cu(II)离子易造成配合物荧光淬灭[Ford, P. C.; Cariati, E.;Bourassa, J.; Chem. Rev.1999, 99, 3625; Pu, L. Chem. Rev.2004,104, 1687;Zhou, Y.; Zhang, J. F.; Yoon, J. Chem. Rev.2014, 114, 5511; Melnic, E.;Coropceanu, E. B.; Kulikova, O. V.; Siminel, A. V.; Anderson, D.; Rivera-Jacquez, H. J.; Masunov, A. E.; Fonari, M. S.; Kravtsov, V. C.; J. Phys. Chem. C2014, 118, 30087]，因此设计合成合适的发光材料的铜配合物是一件很有挑战的工作，迄今为止，见诸文献的报道相对较少[Royzen, M.; Dai, Z.; Canary, J. W. J. Am. Chem. Soc. 2005, 127, 1612; Zhang, X.; Jing, X.; Liu, T.; Han, G.; Li,H.; Duan, C. Inorg. Chem. 2012, 51, 2325; A. K. Jassal, S. Sharma, G. Hundal,M. S. Hundal, Cryst. Growth Des. 2015, 15 , 79]。
发明内容
本发明的目的在于提供一种对苯二甲酸和2,4,5-三(4-吡啶基)-1H -咪唑混配的铜配合物、其制备方法及应用，该铜配合物具有二维44拓扑结构，常温下具有稳定的光学性能，
本发明采用如下技术方案：
一种对苯二甲酸和2,4,5-三(4-吡啶基)-1H -咪唑混配的铜配合物，所述铜配合物的分子式为[Cu2(L)2(Htpim)2(H2O)2]n，其中L为对苯二甲酸阴离子配体，结构式如下：
， Htpim 为2,4,5-三(4-吡啶基)-1H -咪唑[英文名称：2,4,5-tri(4-pyridyl)-1H -imidazole]配体，结构式如下：；所述铜配合物的基本结构为二维44拓扑结构。
进一步地，所述铜配合物的晶体属三斜晶系，空间群为P-1，晶胞参数为：a ＝11.049(2) Å，b ＝ 13.791(3) Å，c ＝ 22.429(5) Å，α = 84.92(3)°，β ＝ 77.23(3)°，γ =76.76(3)°。
上述的对苯二甲酸和2,4,5-三(4-吡啶基)-1H-咪唑混配的铜配合物的制备方法，先加入对苯二甲酸、2,4,5-三(4-吡啶基)-1H-咪唑、以及CuCl2·2H2O，再加入由N,N-二甲基甲酰胺和蒸馏水组成的混合溶剂，调节pH值至3~4，超声震荡后，置于80~90°C的干燥箱中恒温65~80小时，经乙醇洗涤，干燥即得。
具体地，所述对苯二甲酸、2,4,5-三(4-吡啶基)-1H-咪唑和CuCl2·2H2O的摩尔比为1~2：1：1。
具体地，所述混合溶剂中，N,N-二甲基甲酰胺与蒸馏水的体积比为1~2：1。
上述的对苯二甲酸和2,4,5-三(4-吡啶基)-1H-咪唑混配的铜配合物作为荧光材料的应用。
本发明的有益效果如下：
本发明采用低温溶剂热法合成，该方法有别于文献报道中常用的高温水热等方法，克服了温度高、危险性大、产率低、可重复性差等缺点。本发明制备方法工艺简单，条件温和，收率较高、可重复性好，而且所述铜配合物在常温下具有稳定的光学性能，具有灵敏检测亚铁离子Fe2+、铁离子Fe3+的能力，为材料科学领域的发展注入新的活力。
附图说明
图1为所述铜配合物中铜（Cu）离子的配位环境图；
图2为所述铜配合物的二维结构图；
图3为所述铜配合物的XRD图；
图4为所述铜配合物的固体紫外-可见光谱图；
图5为所述铜配合物的固体荧光图；
图6为所述铜配合物在不同阳离子溶液中的荧光发射图。
具体实施方式
为了使本发明的技术目的、技术方案和有益效果更加清楚，下面结合附图和具体实施例对本发明的技术方案作出进一步的说明，但所述实施例旨在解释本发明，而不能理解为对本发明的限制，实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。
实施例1
所述铜配合物的制备过程如下：
首先在玻璃小瓶中加入0.1 mmol对苯二甲酸（济南恒化科技有限公司）、0.05 mmol 2,4,5-三(4-吡啶基)-1H-咪唑（英文名称：2,4,5-tri(4-pyridyl)-1H-imidazole，济南恒化科技有限公司）和0.05 mmol CuCl2·2H2O（济南恒化科技有限公司），然后再用移液枪将2mL混合溶剂（体积比为1：1的N,N-二甲基甲酰胺和蒸馏水的混合溶剂）加入玻璃小瓶中，溶解均匀后，加入质量分数为98%的浓硫酸20µL调节反应液pH至3~4，超声波震荡5min，然后将玻璃小瓶密封，放入85°C的干燥箱中，干燥箱内的加热环境较为均匀，本发明无需真空条件，经过恒温72小时，待其冷却到室温后，观察得到宝蓝色块状晶体，然后经过用无水乙醇洗涤、干燥即得。
所得铜配合物的产率为70％，分子式为：[Cu2(L)2(Htpim)2(H2O)2]n；
主要的红外吸收峰为3437 cm﹣1，2361 cm﹣1，1653 cm﹣1，1616 cm﹣1，1585 cm﹣1，1506 cm﹣1，1374 cm﹣1，1222 cm﹣1，1091 cm﹣1，1066 cm﹣1，967 cm﹣1，881 cm﹣1，823 cm﹣1，756 cm﹣1，668cm﹣1，519 cm﹣1，419 cm﹣1。
所得铜配合物的结构测定：
在显微镜下选取所得铜配合物的合适大小的单晶，使用Mo-Kα 射线(λ= 0.71073 Å)，该射线为经过石墨单色器单色化的，然后室温下经过Bruker APEX II CCD面探衍射仪，通过ω的方式以达到收集衍射数据的目的。然后利用SADABS程序对所有的衍射数据来进行半经验吸收校正。并且使用最小二乘法来确定晶胞参数。还要通过SAINT程序来完成数据的还原，同时利用SHELXTL程序进行结构的解析。实验中使用直接法来解出晶体结构，利用直接法的E-map以达到确定金属原子位置的目的，再利用差值傅立叶函数法以及最小二乘法来确定其他的非氢原子，之后经过各向异性的精修。然后通过理论加氢法就可以确定氢原子位置。详细的所得铜配合物的晶体测定数据见表1，XRD图如图3所示，实验样品的谱图与模拟谱图的特征峰相互对应，结构图如图1，所得铜配合物中两种铜离子的有着类似的配位环境（两种铜离子的配位方式相同，而键长稍有不同），铜离子都是五配位的，并通过双单齿桥联的L配体（L为对苯二甲酸阴离子配体）和μ2-2,4-Npy,Npy双桥联模式的Htpim配体[Htpim为2,4,5-三(4-吡啶基)-1H-咪唑配体]形成如图2所示的二维44拓扑结构。
表1 铜配合物[Cu2(L)2(Htpim)2(H2O)2]n的晶体学数据
由表1可知，所述铜配合物的分子式为C52H38Cu2N10O10，其晶体属三斜晶系，空间群为P-1，晶胞参数为：a ＝ 11.049(2) Å，b ＝ 13.791(3) Å，c ＝ 22.429(5) Å，α = 84.92(3)°，β ＝ 77.23(3)°，γ=76.76(3)°。
所得铜配合物的紫外-可见吸收性质测定：
干燥的铜配合物样品经研磨处理后，进行固体紫外-可见吸收光谱测试，固体紫外-可见光谱图见图4，在226nm，287nm，361nm和640nm 处显示出特征吸收。
所得铜配合物的荧光性质测定：
干燥的铜配合物样品经研磨处理后，进行荧光测试，固体荧光谱图如图5所示，在Ex为227 nm处激发，在Em为391 nm处得到发射峰。
实施例2
所述铜配合物的制备过程如下：
首先在玻璃小瓶中加入0.05 mmol对苯二甲酸（济南恒化科技有限公司）、0.05 mmol2,4,5-三(4-吡啶基)-1H-咪唑（英文名称：2,4,5-tri(4-pyridyl)-1H-imidazole，济南恒化科技有限公司）和0.05 mmol CuCl2·2H2O（济南恒化科技有限公司），然后再用移液枪将2mL混合溶剂（体积比为2：1的N,N-二甲基甲酰胺和蒸馏水的混合溶剂）加入玻璃小瓶中，溶解均匀后，加入98%的浓硫酸20µL调节反应液pH至3~4，超声波震荡5min，然后将玻璃小瓶密封，放入80°C的干燥箱中，干燥箱内的加热环境较为均匀，本发明无需真空条件，经过恒温80小时，待其冷却到室温后，观察得到宝蓝色块状晶体，然后经过用无水乙醇洗涤、干燥即得。所得铜配合物的产率为60％。
应用试验1
将本发明实施例1所得铜配合物（即下述样品）作为发光材料进行阳离子荧光化学传感应用试验。
试验方法
下述浓度均为 0.01 mol/L的各种硝酸盐M(NO3)x的N,N-二甲基甲酰胺（DMF）溶液：M =钠离子Na+，镁离子Mg2+，铝离子Al3+，钾离子K+，钙离子Ca2+，镉离子Cd2+，锰离子Mn2+，铁离子Fe3+，亚铁离子Fe2+，钴离子Co2+，镍离子Ni2+，铜离子Cu2+，锌离子Zn2+，每种硝酸盐溶液均取2mL并各加入 4 mg样品，为保证分散均匀，超声波处理30分钟，然后分别通过荧光分析仪（Cary Eclipse EL06053221）进行荧光测试。结果如图6所示，可以看出，镁离子Mg2+，钠离子Na+，钾离子K+，钙离子Ca2+增强了铜配合物的荧光强度，而锰离子Mn2+，钴离子Co2+，镍离子Ni2+，铜离子Cu2+，亚铁离子Fe2+，铁离子Fe3+却大大减弱了铜配合物的荧光，特别是亚铁离子Fe2+，铁离子Fe3+使铜配合物荧光几乎完全淬灭，由此可知，所述铜配合物具有灵敏检测亚铁离子Fe2+，铁离子Fe3+的能力，可以作为荧光材料使用。
最后所应说明的是：上述实施例仅用于说明而非限制本发明的技术方案，任何对本发明进行的等同替换及不脱离本发明精神和范围的修改或局部替换，其均应涵盖在本发明权利要求保护的范围之内。
Claims (6)
1.一种对苯二甲酸和2,4,5-三(4-吡啶基)-1H - 咪唑混配的铜配合物，其特征在于，所述铜配合物的分子式为[Cu2(L)2(Htpim)2(H2O)2]n，其中L为对苯二甲酸阴离子配体，结构式如下：，
Htpim 为2,4,5-三(4-吡啶基)-1H - 咪唑配体，结构式如下：
。
2.根据权利要求1所述的对苯二甲酸和2,4,5-三(4-吡啶基)-1H - 咪唑混配的铜配合物，其特征在于，所述铜配合物的晶体属三斜晶系，空间群为P-1，晶胞参数为：a ＝ 11.049(2) Å，b ＝ 13.791(3) Å，c ＝ 22.429(5) Å，α = 84.92(3)°，β ＝ 77.23(3)°，γ =76.76(3)°。
3.根据权利要求1所述的对苯二甲酸和2,4,5-三(4-吡啶基)-1H - 咪唑混配的铜配合物的制备方法，其特征在于，先加入对苯二甲酸、2,4,5-三(4-吡啶基)-1H -咪唑、以及CuCl2·2H2O，再加入由N,N-二甲基甲酰胺和蒸馏水组成的混合溶剂，调节pH值至3~4，超声震荡后，置于80~90°C的干燥箱中恒温65~80小时，经乙醇洗涤，干燥即得。
4.根据权利要求3所述的对苯二甲酸和2,4,5-三(4-吡啶基)-1H -咪唑混配的铜配合物的制备方法，其特征在于，所述对苯二甲酸、2,4,5-三(4-吡啶基)-1H -咪唑和CuCl2·2H2O的摩尔比为1~2：1：1。
5.根据权利要求3或4所述的对苯二甲酸和2,4,5-三(4-吡啶基)-1H -咪唑混配的铜配合物的制备方法，其特征在于，所述混合溶剂中，N,N-二甲基甲酰胺与蒸馏水的体积比为1~2：1。
6.根据权利要求1所述的对苯二甲酸和2,4,5-三(4-吡啶基)-1H -咪唑混配的铜配合物作为荧光材料的应用。
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| CN109678865A (zh) * | 2018-12-06 | 2019-04-26 | 安阳师范学院 | 无机有机杂化铜碘化合物、其制备方法及作为荧光温度传感材料的应用 |
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| CN109678865A (zh) * | 2018-12-06 | 2019-04-26 | 安阳师范学院 | 无机有机杂化铜碘化合物、其制备方法及作为荧光温度传感材料的应用 |
| CN109678865B (zh) * | 2018-12-06 | 2021-03-16 | 安阳师范学院 | 无机有机杂化铜碘化合物、其制备方法及作为荧光温度传感材料的应用 |
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