CN106544737B - 一种u型不对称的非线性光学无机-有机杂化材料的制备方法 - Google Patents
一种u型不对称的非线性光学无机-有机杂化材料的制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000003643 water by type Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 14
- 239000003446 ligand Substances 0.000 abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052968 proustite Inorganic materials 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- WBPWDGRYHFQTRC-UHFFFAOYSA-N 2-ethoxycyclohexan-1-one Chemical compound CCOC1CCCCC1=O WBPWDGRYHFQTRC-UHFFFAOYSA-N 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- YFDLHELOZYVNJE-UHFFFAOYSA-L mercury diiodide Chemical compound I[Hg]I YFDLHELOZYVNJE-UHFFFAOYSA-L 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
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Abstract
本发明涉及光学性质领域,具体是一种U型不对称的非线性光学无机‑有机杂化材料的制备方法。步骤包括:将0.7~1.3mmolCaCl2、0.7~1.3mmol间苯二甲酸‑5‑磺酸钠、1.8~2.2mmol 1,10‑邻菲罗啉、0.08~0.12mL 1M的NaOH和13~15 mL去离子水放入反应釜中,155~165℃加热4~7d后冷却过滤,得到块状无色晶体。与现有技术相比,比本发明具有以下优点:将非线性光学性质的材料由无机材料扩展成无机‑有机杂化材料;利用具有对称结构的配体与钙金属离子进行合成;利用对称性的配体构筑成不对称的配合物,具有非线性光学性质。
Description
技术领域
本发明涉及光学性质领域,具体是一种U型不对称的非线性光学无机-有机杂化材料的制备方法。
背景技术
现有的二阶非线性光学材料多集中在碘酸锂、铌酸锂等以及半导体晶体,如碲和淡红银矿(Ag3AsS3)等无机化合物。
如中国专利申请CN 105568380 A《一种新型红外非线性光学材料及其制备方法与应用》,其公开了一种新型红外非线性光学材料,其分子式为RbHgI3,该材料的突出特点是有较大的可相位匹配的二阶非线性光学系数,在紫外、可见光区和红外光区有很宽的透光窗口且具有良好的热稳定性,合成方法为将RbI和HgI2(摩尔比1 :1) 加入到有机溶剂中,在80℃下搅拌,至成为澄清透明的溶液,继续搅拌24小时,反应结束后自然冷却,通过室温下缓慢挥发法或缓慢降温方法,得到黄色透明的晶体。
中国专利申请CN 105384760 A公开了一种手性Cu(II) 配位聚合物及其制备方法,其化学式为{Cu[(1R,2R)-3-bcpb]Cl2}n,制备方法为称取CuCl2.2H2O 以及(1R,2R)-3-bcpb 加入到CH3OH 溶液中,制得悬浊液,将该悬浊液转移到反应釜中反应后制得手性Cu(II) 配位聚合物,其具有良好的二阶非线性光学活性性能。
但在现有技术中对无机-有机杂化材料鲜有研究,尤其是利用具有对称结构的配体与钙金属离子进行合成,构筑成不对称的配合物方面报道甚少。
发明内容
本发明利用具有对称结构的配体与钙金属离子进行合成,构筑成不对称的配合物。
本发明是通过以下技术方案实现的:
一种U型不对称的非线性光学无机-有机杂化材料的制备方法,步骤包括:将0.7~1.3 mmol CaCl2、0.7~1.3 mmol间苯二甲酸-5-磺酸钠、1.8~2.2 mmol 1,10-邻菲罗啉、0.08~0.12 mL 1M 的NaOH和13~15 mL去离子水放入反应釜中,155~165 ℃加热4~7 d后冷却过滤,得到块状无色晶体。
优选的步骤包括:将1 mmol CaCl2、1 mmol间苯二甲酸-5-磺酸钠、2 mmol 1,10-邻菲罗啉、0.1 mL 1M 的NaOH和15 mL去离子水放入反应釜中,160 ℃加热5 d后冷却过滤,得到块状无色晶体。
配合物的结构为不对称的U型结构。三个配体桥连四个钙离子形成U型的结构。钙离子是八配位的,配位点由1,10-邻菲罗啉的四个氮原子和两个水分子以及配体的两个羧基氧原子占据。
本发明利用碱土元素合成配合物,其具有非线性光学性质。合成得到的配合物具有非线性光学性质,其强度是KH2PO4的3倍,还具有相位匹配(图4)。同时还具有荧光发射性质。配合物1的荧光发射峰在409 nm和463 nm,配体的发射峰在356 nm。配合物1的发射峰与配体相比,发生了红移,红移至少为50 nm(图3)。配合物1在276 °C之前结构保持稳定(图2)。
与现有技术相比,比本发明具有以下优点:
(1)将非线性光学性质的材料由无机材料扩展成无机-有机杂化材料;
(2)利用具有对称结构的配体与钙金属离子进行合成;
(3)合成的材料具有多功能性,不但具有非线性光学性质,还具有荧光性质;
(4)利用对称性的配体构筑成不对称的配合物,具有非线性光学性质;
(5)合成方法简单,条件温和,容易控制。
附图说明
图1为本发明配合物1分子结构图;
图2为本发明配合物1的热重曲线;
图3为本发明荧光发射光谱;
图4为本发明配合物1的相位匹配曲线;
图3中,NaH2SIP、间苯二甲酸-5-磺酸钠,complex、配合物1。
具体实施方式
下面结合实施例对本发明做进一步详细说明,但本发明的保护范围不受实施例所限。
实施例1:
将1 mmol CaCl2、1 mmol间苯二甲酸-5-磺酸钠、2 mmol 1,10-邻菲罗啉、0.1 mL1M 的NaOH和15 mL去离子水放入反应釜中,160 ℃加热5 d后冷却过滤,得到块状无色晶体配合物1,产率为73%。
实施例2:
将0.7 mmol CaCl2、1 mmol间苯二甲酸-5-磺酸钠、1.8 mmol 1,10-邻菲罗啉、0.08 mL 1M 的NaOH和13 mL去离子水放入反应釜中,155℃加热4 d后冷却过滤,得到块状无色晶体,产率为70%。
实施例3:
将1.3 mmol CaCl2、1 mmol间苯二甲酸-5-磺酸钠、2 mmol 1,10-邻菲罗啉、0.12mL 1M 的NaOH和15 mL去离子水放入反应釜中,160℃加热5 d后冷却过滤,得到块状无色晶体,产率为70%。
实施例4:
将1.3 mmol CaCl2、0.7 mmol间苯二甲酸-5-磺酸钠、2.2 mmol 1,10-邻菲罗啉、0.1 mL 1M 的NaOH和14 mL去离子水放入反应釜中,165℃加热7d后冷却过滤,得到块状无色晶体,产率为72%。
实施例5:
将1.1 mmol CaCl2、0.9 mmol间苯二甲酸-5-磺酸钠、1.8 mmol 1,10-邻菲罗啉、0.08 mL 1M 的NaOH和15 mL去离子水放入反应釜中,160℃加热6d后冷却过滤,得到块状无色晶体,产率为69%。
实施例6:
将0.8 mmol CaCl2、1 mmol间苯二甲酸-5-磺酸钠、2 mmol 1,10-邻菲罗啉、0.09mL 1M 的NaOH和15 mL去离子水放入反应釜中,165℃加热7d后冷却过滤,得到块状无色晶体,产率为72%。
Claims (2)
1.一种U型不对称的非线性光学无机-有机杂化材料的制备方法,其特征在于步骤包括:将0.7~1.3 mmol CaCl2、0.7~1.3 mmol间苯二甲酸-5-磺酸钠、1.8~2.2 mmol 1,10-邻菲罗啉、0.08~0.12 mL 1M 的NaOH和13~15 mL去离子水放入反应釜中,155~165 ℃加热4~7d后冷却过滤,得到块状无色晶体。
2.如权利要求1所述的一种U型不对称的非线性光学无机-有机杂化材料的制备方法,其特征在于步骤包括:将1 mmol CaCl2、1 mmol间苯二甲酸-5-磺酸钠、2 mmol 1,10-邻菲罗啉、0.1 mL 1M 的NaOH和15 mL去离子水放入反应釜中,160 ℃加热5 d后冷却过滤,得到块状无色晶体。
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