CN105820347B - 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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- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 10
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- 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 claims description 2
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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%。
）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
。
）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。
）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1064nm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；
该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°。
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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