CN105820347A - 一种三维配位聚合物非线性光学材料及其制备方法 - Google Patents
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 25
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 10
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 10
- 239000011565 manganese chloride Substances 0.000 claims description 10
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 abstract description 5
- 238000004891 communication Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 abstract description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- WABCMZMPPSJIPZ-UHFFFAOYSA-N 2-pyridin-4-yl-1h-imidazole-4,5-dicarboxylic acid Chemical compound N1C(C(O)=O)=C(C(=O)O)N=C1C1=CC=NC=C1 WABCMZMPPSJIPZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000001450 anions Chemical class 0.000 abstract 1
- 230000009022 nonlinear effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229950000845 politef Drugs 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004836 empirical method Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
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Abstract
本发明属于过渡金属配位聚合物领域,具体涉及一种三维无心配位聚合物非线性光学材料,其化学式为{[Mn(HPIDC)(H2O)]·2H2O}n,其中HPIDC为2‑(4‑吡啶基)‑1H‑咪唑‑4,5‑二羧酸的二价阴离子。本发明提供的三维配位聚合物其二次谐波效应(SHG)是标准样品磷酸二氢钾(KDP)的1.5倍,具有一定的二阶非线性性质,有希望作为一种非线性光学材料,在光信息存储、激光通讯、电子仪器以及医药器材等领域有广阔的应用前景。
Description
技术领域
本发明属于过渡金属配位聚合物材料技术领域,具体涉及一种三维配位聚合物非线性光学材料及其制备方法。
背景技术
随着光电子技术的蓬勃发展,非线性光学晶体材料在通信、激光、光信息存储等领域有着广阔的应用前景。配位聚合物结合了无机和有机非线性材料的优势,能够调控金属中心的几何构型和金属-有机配体的配位方向性,定向合成非心对称的骨架材料,成为非线性光学的研究热点。近年来,配位聚合物作为非线性光学材料的研究已取得了一些进展(YeQiong,Li Yong-Hua,Song Yu-Mei,Huang Xue-Feng,Xiong Ren-Gen,Xue Ziling,Inorg.Chem.,2005,44,618;Dang Song,Zhang Jian-Han,Sun Zhong-Ming,Zhang Hongjie,Chem.Commun.,2012,48,11139;Wang Cheng,Zhang Teng,Lin Wenbin,Chem. Rev.,2012,112,1084;He Yan-Ping,Tan Yan-Xi,Zhang Jian,Inorg. Chem.,2015,54,6653)。然而,如何有效调控非心配位聚合物的合成及其作为非线性光学材料的实际应用还是一个很大的挑战。因此,对于配位聚合物非线性光学材料的研究和探索,具有十分重要的意义。
发明内容
本发明目的在于提供一种三维配位聚合物非线性光学材料及其制备方法。
为实现上述目的,本发明采用如下技术方案:
一种三维配位聚合物非线性光学材料,其化学式为{[Mn(HPIDC)(H2O)]·2H2O}n,其中,HPIDC为2-(4-吡啶基)-1H-咪唑-4,5-二羧酸的二价阴离子。其结构式见图1。
上述的三维配位聚合物非线性光学材料,晶体属于正交晶系,空间群为Pna21,晶胞参数为:a = 7.8401(5) Å,b = 10.3176(7) Å,c = 15.8809(11) Å,α= 90°,β= 90 °,γ= 90°。所述三维配位聚合物非线性光学材料的三维网络结构图见图2。
上述三维配位聚合物非线性光学材料的制备方法,其以水为溶剂,将2-(4-吡啶基)-1H-咪唑-4,5-二羧酸、硫氰酸钾和氯化锰混合后在水热条件下反应制成;具体为:将2-(4-吡啶基)-1H-咪唑-4,5-二羧酸、硫氰酸钾和MnCl2·4H2O加入水中,搅拌15-20 min,然后在160℃-180℃下恒温密闭2-4天,冷却至室温,过滤、洗涤、干燥,即得。
具体的,2-(4-吡啶基)-1H-咪唑-4,5-二羧酸与硫氰酸钾、MnCl2·4H2O的摩尔比为0.5-0.6:0.8-1:1,每摩尔MnCl2·4H2O对应加入5-7L水。
和现有技术相比,本发明的有益效果:
本发明三维Mn(II)配位聚合物属于无心空间群,其二次谐波效应(SHG)是标准样品磷酸二氢钾(KDP)的1.5倍,具有一定的二阶非线性性质,有希望作为一种非线性光学材料,在光信息存储、激光通讯、电子仪器以及医药器材等领域有广阔的应用前景。此外,本发明制备工艺简单,收率高达65%。
附图说明
图1为本发明三维配位聚合物非线性光学材料的结构图;
图2为本发明三维配位聚合物非线性光学材料的三维网络结构图;
图3为本发明三维配位聚合物非线性光学材料的红外光谱图;
图4为本发明三维配位聚合物非线性材料的二次谐波(SHG)信号。
具体实施方式
以下结合实施例对本发明的技术方案作进一步地详细介绍,但本发明的保护范围并不局限于此。
实施例1
取2-(4-吡啶基)-1H-咪唑-4,5-二羧酸(0.5mmol)、硫氰酸钾(1mmol)和MnCl2·4H2O(1mmol)加入6毫升的水中,搅拌20分钟,然后密封于25毫升聚四氟乙烯反应釜中,在160℃下恒温密闭3天,冷却至室温后,过滤、洗涤、干燥,得到黄色块状晶体,收率为64%。
实施例2
取2-(4-吡啶基)-1H-咪唑-4,5-二羧酸(0.5mmol)、硫氰酸钾(0.8mmol)和MnCl2·4H2O(1mmol)加入5毫升的水中,搅拌20分钟,然后密封于25毫升聚四氟乙烯反应釜中,在170℃下恒温密闭3天,冷却至室温后,过滤、洗涤、干燥,得到黄色块状晶体,收率为27%。
实施例3
取2-(4-吡啶基)-1H-咪唑-4,5-二羧酸(0.6mmol)、硫氰酸钾(1mmol)和MnCl2·4H2O(1mmol)加入7毫升的水中,搅拌20分钟,然后密封于25毫升聚四氟乙烯反应釜中,在180℃下恒温密闭3天,冷却至室温后,过滤、洗涤、干燥,得到黄色块状晶体,收率为21%。
1)晶体结构测定:
选取上述制备得到的晶体用于结构分析,在296±2K下在Bruker Apex-II CCD衍射仪上,采用石墨单色化的Mo Kα射线(λ = 0.71073 Å),在2.35°<θ<25°的范围内收集晶体衍射点数据,晶体结构由经验法解出,配合物中所有的非氢原子的坐标用全矩阵最小二乘法进行各向异性温度因子修正,所有的氢原子坐标由理论加氢程序找出。配合物的晶体学数据见下表1:
表1
。
2)红外光谱测定:
用溴化钾压片法在400~4000 cm–1范围内使用德国Bruker VERTEX70傅里叶红外光谱仪测定。所得配位配合物的主要红外吸收峰(见图3)为:3373 cm–1,1621 cm–1,1601 cm–1,1538 cm–1,1486 cm–1,1447 cm–1,1422 cm–1,1381 cm–1,1230 cm–1,1110 cm–1,1012 cm–1,864 cm–1,817 cm–1。其中,3373 cm–1处的峰可以归属于水分子中羟基的伸缩振动,1621 cm–1和1381 cm–1处的峰可以归属于羧基的不对称和对称伸缩振动。
3)二阶非线性光学效应测试:
采用的是Kurtz−Perry粉末倍频技术,使用Nd:YAG脉冲激光器产生的波长为1064 nm的基频光作为光源,测试结果见图4。由图4可以看出:该配位聚合物的二次谐波(SHG)信号是标准样品磷酸二氢钾(KDP)的1.5倍,表现出一定的二阶非线性性质,有希望作为一种非线性光学材料,在光信息存储、激光通讯、电子仪器以及医药器材等领域有广阔的应用前景。
上述实施例为本发明优选的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明所作的改变均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (3)
1.一种三维配位聚合物非线性光学材料,其特征在于,其化学式为{[Mn(HPIDC)(H2O)]·2H2O}n,其中HPIDC为2-(4-吡啶基)-1H-咪唑-4,5-二羧酸的二价阴离子。
2.权利要求1所述三维配位聚合物非线性光学材料的制备方法,其特征在于,将2-(4-吡啶基)-1H-咪唑-4,5-二羧酸、硫氰酸钾和MnCl2·4H2O加入水中,搅拌15-20 min,然后在160℃-180℃下恒温密闭2-4天,冷却至室温,过滤、洗涤、干燥,即得。
3.如权利要求2所述三维配位聚合物非线性光学材料的制备方法,其特征在于,2-(4-吡啶基)-1H-咪唑-4,5-二羧酸与硫氰酸钾、MnCl2·4H2O的摩尔比为0.5-0.6:0.8-1:1,每摩尔MnCl2·4H2O对应加入5-7L水。
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CN106432325A (zh) * | 2016-09-22 | 2017-02-22 | 济南大学 | 一种黄色光致发光的非线性光学晶体材料及其制备与应用 |
CN106633096A (zh) * | 2017-01-09 | 2017-05-10 | 山西大学 | 一种双核铕(iii)配位聚合物及其制备方法与应用 |
CN112920422A (zh) * | 2021-02-03 | 2021-06-08 | 江南大学 | 一种杂金属簇基金属有机框架晶体材料、制备方法及其应用 |
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CN106432325A (zh) * | 2016-09-22 | 2017-02-22 | 济南大学 | 一种黄色光致发光的非线性光学晶体材料及其制备与应用 |
CN106432325B (zh) * | 2016-09-22 | 2019-01-04 | 济南大学 | 一种黄色光致发光的非线性光学晶体材料及其制备与应用 |
CN106633096A (zh) * | 2017-01-09 | 2017-05-10 | 山西大学 | 一种双核铕(iii)配位聚合物及其制备方法与应用 |
CN112920422A (zh) * | 2021-02-03 | 2021-06-08 | 江南大学 | 一种杂金属簇基金属有机框架晶体材料、制备方法及其应用 |
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