CN108690055A - 一种钡的配合物及其制备方法和应用 - Google Patents
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- 229910052788 barium Inorganic materials 0.000 title claims abstract description 29
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000002923 oximes Chemical class 0.000 claims abstract description 15
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZSKGQVFRTSEPJT-UHFFFAOYSA-N pyrrole-2-carboxaldehyde Chemical compound O=CC1=CC=CN1 ZSKGQVFRTSEPJT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 125000004429 atom Chemical group 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001422 barium ion Inorganic materials 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 206010011224 Cough Diseases 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
本发明提供了一种钡的配合物及其制备方法,涉及配合物荧光材料领域。钡的配合物的化学式为:HBa3(pda)3(H2O)3Cl,其中pda2‑为吡咯‑2,6‑二羧酸酸根。所述配合物的制备方法:第一步,在2‑吡咯甲醛肟乙醇溶液加入固态吡咯‑2,6‑二羧酸、氯化钡,加热得到白色沉淀,第二步,加水,白色沉淀转化为目标配合物。本发明配合物具有良好的荧光性能,热稳定性好,制备方法简单。
Description
技术领域
本发明涉及金属配合物荧光材料领域,具体涉及一种钡的配合物及其制备方法。
背景技术
高发光性能的荧光配合物在通讯、卫星、雷达、光学计算机和生物分子探针等领域具有巨大的应用前景,因此,这类功能性配合物的分子设计、合成及性质研究具有重要意义。其中碱土金属-有机配位聚合物由于其具有良好的荧光性能得到了广泛的关注。
钡的配合物材料已经被报道,钡离子是一种碱土金属,有非常大的离子半径,可以与配体形成高配合数的配体,钡与配合物复杂的结合,并由不同的结构呈现出不同的性质,展现出优良的潜在性能。吡咯-2,5-二羧酸酸根是一种配体,可以与金属桥连。目前,利用钡、吡咯-2,5-二羧酸制备钡的配合物尚未见报道。
发明内容
要解决的技术问题:本发明的目的是提供一种具有良好的荧光性能,热稳定性好,制备方法简单的钡的配合物及其制备方法。
技术方案:一种钡的配合物,钡的配合物的化学式为:HBa3(pda)3(H2O)3Cl,其中pda2-为吡咯-2,6-二羧酸酸根。
进一步的,所述钡的配合物的结构为氯桥连的三维结构,属于R-3空间群,三方晶系,为不对称单元,其晶胞参数为:a=14.484(4)Å,b=14.484(4) Å,c=21.970(2) Å,α=90︒,β=90︒,γ=120︒。在不对称单元中,有三个BaII离子,三个pda2-阴离子,三个配位水分子,一个Cl-离子;每一个BaII离子连接着四个pda2-配体中的六个氧(O1, O1B, O2C, O3, O3A, O4A)原子和一个N(N1)原子,一个水分子(O5)和C11原子,所述BaII离子的构型是一个扭曲的单帽四方反棱柱体;Ba-O的键长从2.623(4)到2.745(4) Å,Ba-N的键长是2.687(5) Å; Cl-与三个钡离子组成三角锥结构,每一个Ba-Cl距离是2.9860(13) Å,Ba-Cl-Ba的键角是114.87(7)o;BaII离子通过O1和O3原子连接到相邻的三个BaII离子上,Ba与Ba的距离在4.439到5.095 Å之间;在晶体结构中,pda2-配体显示µ 4-η 1:η 2:η 1:η 1:η 1配位模式,并且连接4个BaII离子形成一个三维网状结构。
上述的一种钡的配合物的制备方法,包括以下步骤:
S1.将2-吡咯甲醛肟乙醇溶液中加入固体吡咯-2,6-二羧酸、氯化钡,加热,得到白色沉淀;
S2.将白色沉淀中加入水,白色沉淀即转化为目标配合物,过滤,洗涤,获得产品[HBa3(pda)3(H2O)3Cl]n。
进一步的,所述步骤S1中2-吡咯甲醛肟乙醇溶液的浓度为0.08-0.12 mol/L,每升2-吡咯甲醛肟乙醇溶液中加入吡咯-2,6-二羧酸和氯化钡的量分别为0.025-0.035 mol和0.045-0.055 mol,且加热温度控制 在80-100℃范围内。
进一步的,所述步骤S2中的加水量与步骤S1中2-吡咯甲醛肟乙醇溶液的体积比为0.35-0.45:1。
进一步的,所述步骤S1中2-吡咯甲醛肟乙醇溶液的浓度为0.10 mol/L,每升2-吡咯甲醛肟乙醇溶液中加入吡咯-2,6-二羧酸和氯化钡的量分别为0.03 mol和0.05 mol,且加热温度控制在90℃。
进一步的,所述步骤S2中的加水量与步骤S1中2-吡咯甲醛肟乙醇溶液的体积比为0.4:1。
上述的一种钡的配合物在荧光材料领域的应用。
有益效果:本发明的钡的配合物具有以下优点:
本发明制备的配合物具有良好的荧光性能,与配体的荧光最大发射波长接近,可以作为荧光材料在材料领域得到应用。其热分析数据显示,该配合物加热后可失去结晶水和侨联的Cl-离子,但骨架直到550℃左右仍保持稳定,说明其具有良好的热稳定性,为其作为荧光材料的进一步开发应用提供了保证。
附图说明
图1为实施例1制备的Ba-吡咯2,5二羧酸配合物的配位结构示意图;
图2为实施例1制备的Ba-吡咯2,5二羧酸配合物的粉末X-射线衍射图;
图3为实施例1制备的Ba-吡咯2,5二羧酸配合物的固态荧光光谱图。
具体实施方式
实施例1
S1. 在100 ml浓度为0.1 mol/L的2-吡咯甲醛肟乙醇溶液,加入固体吡咯-2,5-二羧酸0.003 mol、氯化钡0.005 mol,加热,在80℃条件下搅拌,得到白色沉淀;
S2. 继续加水40 mL,白色沉淀转化为目标配合物,过滤,洗涤,获得产品HBa3(pda)3(H2O)3Cl,所得产品配位结构意图如图1所示,X-射线粉末衍射图参见图2,该配位聚合物具有良好的发光性能,荧光光谱图如图3所示,其在激发波长为275 nm的光源激发下,其发射光谱最大值为500 nm。
实施例2
S1. 在100 ml浓度为0.08 mol/L的2-吡咯甲醛肟乙醇溶液加入固体吡咯-2,5-二羧酸0.0025 mol、氯化钡0.0045 mol,加热,在温度90℃条件下搅拌,得到白色沉淀;
S2. 继续加水35mL,白色沉淀转化为目标配合物,过滤,洗涤,获得产品HBa3(pda)3(H2O)3Cl。
实施例3
S1. 在100 ml浓度为0.12 mol/L的2-吡咯甲醛肟乙醇溶液加入固体吡咯-2,5-二羧酸0.0035 mol、氯化钡0.0055 mol,加热至温度100℃,搅拌,得到白色沉淀,
S2. 继续加水45mL,白色沉淀转化为目标配合物,过滤,洗涤,获得产品HBa3(pda)3(H2O)3Cl。
上述实施例制得的钡的配合物的化学式为:HBa3(pda)3(H2O)3Cl,其中pda2-为吡咯-2,5-二羧酸酸根;结构为氯桥连的三维结构,属于R-3空间群,三方晶系;其晶胞参数为:a=14.484(4)Å,b=14.484(4) Å,c=21.970(2) Å,α=90︒,β=90︒,γ=120︒。在不对称单元中,有三个BaII离子,三个pda2-阴离子,三个配位水分子,一个Cl-离子;每一个BaII离子连接着四个pda2-配体中的六个氧(O1 ,O1B,O2C,O3,O3A,O4A)原子和一个N(N1)原子,一个水分子(O5)和C11原子,所述BaII离子的构型是一个扭曲的单帽四方反棱柱体;Ba-O的键长从2.623(4)到2.745(4) Å,Ba-N的键长是2.687(5) Å;Cl-与三个钡离子组成三角锥结构,每一个Ba-Cl距离是2.9860(13) Å,Ba-Cl-Ba的键角是114.87(7)o;BaII离子通过O1和O3原子连接到相邻的三个BaII离子上,Ba与Ba的距离在4.439到5.095 Å之间;在晶体结构中,pda2-配体显示µ 4-η 1:η 2:η 1:η 1:η 1配位模式,并且连接4个BaII离子形成一个三维网状结构。
Claims (8)
1.一种钡的配合物,其特征在于:钡的配合物的化学式为:HBa3(pda)3(H2O)3Cl,其中pda2-为吡咯-2,6-二羧酸酸根。
2.根据权利要求1所述的一种钡的配合物,其特征在于:所述钡的配合物的结构为氯桥连的三维结构,属于R-3空间群,三方晶系,为不对称单元,在不对称单元中,有三个BaII离子,三个pda2-阴离子,三个配位水分子,一个Cl-离子;每一个BaII离子连接着四个pda2-配体中的六个氧原子和一个N原子,一个水分子和C1-离子,所述BaII离子的构型是一个扭曲的单帽四方反棱柱体;在晶体结构中,pda2-配体连接4个BaII离子形成一个三维网状结构。
3.如权利要求1所述的一种钡的配合物的制备方法,其特征在于,包括以下步骤:
S1.将2-吡咯甲醛肟乙醇溶液中加入固体吡咯-2,6-二羧酸、氯化钡,加热,得到白色沉淀;
S2.将白色沉淀中加入水,白色沉淀即转化为目标配合物,过滤,洗涤,获得产品[HBa3(pda)3(H2O)3Cl]n。
4.根据权利要求3所述的一种钡的配合物的制备方法,其特征在于:所述步骤S1中2-吡咯甲醛肟乙醇溶液的浓度为0.08-0.12 mol/L,每升2-吡咯甲醛肟乙醇溶液中加入吡咯-2,6-二羧酸和氯化钡的量分别为0.025-0.035 mol和0.045-0.055 mol,且加热温度控制 在80-100℃范围内。
5.根据权利要求3所述的一种钡的配合物的制备方法,其特征在于:所述步骤S2中的加水量与步骤S1中2-吡咯甲醛肟乙醇溶液的体积比为0.35-0.45:1。
6.根据权利要求4所述的一种钡的配合物的制备方法,其特征在于:所述步骤S1中2-吡咯甲醛肟乙醇溶液的浓度为0.10 mol/L,每升2-吡咯甲醛肟乙醇溶液中加入吡咯-2,6-二羧酸和氯化钡的量分别为0.03 mol和0.05 mol,且加热温度控制 在90℃。
7.根据权利要求5所述的一种钡的配合物的制备方法,其特征在于:所述步骤S2中的加水量与步骤S1中2-吡咯甲醛肟乙醇溶液的体积比为0.4:1。
8.如权利1-7任一项所述的一种钡的配合物在荧光材料领域的应用。
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