CN105585586A - 一种具有荧光性的苯并咪唑类镉配合物及制备方法和应用 - Google Patents
一种具有荧光性的苯并咪唑类镉配合物及制备方法和应用 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- WALZARNTJFXYNF-UHFFFAOYSA-N 1H-benzimidazole cadmium Chemical compound [Cd].N1=CNC2=C1C=CC=C2 WALZARNTJFXYNF-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 abstract description 4
- 150000001556 benzimidazoles Chemical class 0.000 abstract 3
- HIJZTIRJZAYNGD-UHFFFAOYSA-N 1-[1-(pyridin-4-ylmethyl)benzimidazol-2-yl]ethanol Chemical compound N1=CC=C(C=C1)CN1C(=NC2=C1C=CC=C2)C(C)O HIJZTIRJZAYNGD-UHFFFAOYSA-N 0.000 abstract 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 abstract 2
- -1 cadmium (II) ions Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 229910052793 cadmium Inorganic materials 0.000 description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 238000001338 self-assembly Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
本发明涉及镉配合物，具体涉及一种苯并咪唑类镉配合物，特别是一种基于镉(II)离子和1-(1-(4-吡啶基甲基)-1H-苯并咪唑－2－基)乙醇构筑的具有荧光性的镉配合物及制备方法和应用。本发明提供的一种苯并咪唑衍生物镉配合物，化学式为：{[Cd1.5(μ2-HPyBIE)Br3]·2H2O}n，其中HPyBIE代表1-(1-(4-吡啶基甲基)-1H-苯并咪唑－2－基)乙醇。本发明涉及一种苯并咪唑衍生物镉配合物的制备方法，包括下述步骤：(1)将摩尔比为1:1～2的HPyBIE配体和CdBr2分别溶解于乙醇和甲醇溶液中，将二者混合；(2)室温下搅拌均匀，将溶液置于反应釜中，放于烘箱内，恒温120℃反应72小时，以5℃/h的速度降至室温，有黄色块状晶体析出，过滤，收集产品制成。
Description
技术领域
本发明涉及镉配合物，具体涉及一种苯并咪唑类镉配合物，特别是一种基于镉(II)离子和1-(1-(4-吡啶基甲基)-1H-苯并咪唑－2－基)乙醇构筑的具有荧光性的镉配合物及制备方法和应用。
背景技术
过渡金属配位聚合物由于具有光、电、磁等多种特性，在催化、发光、生物医药等领域表现出广阔的应用前景。苯并咪唑及其衍生物是一类具有较强配位能力、灵活多变配位模式的有机桥联配体，可以与金属离子进行自组装得到多种新颖结构的配合物。苯并咪唑类的小分子作为配体而制得的有机金属配合物，大多具有良好的光致发光和电致发光性能，在光电功能材料领域逐渐受到人们的重视，有关合成和性质的研究日益活跃。1-(1-(4-吡啶基甲基)-1H-苯并咪唑－2－基)乙醇，本身具有良好的发光性能，特别是当其与具有d10电子结构的金属离子配位形成配合物后，在荧光性能方面有着很高的应用价值。
发明内容
本发明是针对上述现状，提供一种具有荧光性能的苯并咪唑类镉配合物及其制备方法。
本发明提供的一种苯并咪唑衍生物镉配合物，化学式为：{[Cd1.5(μ2-HPyBIE)Br3]·2H2O}n，其中HPyBIE代表1-(1-(4-吡啶基甲基)-1H-苯并咪唑－2－基)乙醇。该配合物的晶体属于单斜晶系，空间群为P21/c，晶胞参数： α＝γ＝90°，β＝116.212(8)°。该配合物是二维网状结构，一个不对称单元中包含一个半的镉离子、一个HPyBIE配体、三个配位的溴离子、和两个自由的水分子。金属Cd(II)离子有两种配位模式，其中金属Cd2(II)离子处于[CdNOBr3]的五配位环境中，分别与三个溴离子、同一个HPyBIE配体上的苯并咪唑N原子和羟基O原子配位，构成了四方锥形的模式。金属Cd1(II)离子则采用六配位的模式配位，其中水平位置被四个溴离子占据，而轴向位置被两个不同HPyBIE配体上的吡啶N原子占据，形成了[CdN2Br4]的变形八面体构型。其中Cd-N的键长为2.241(4)和而Cd-Br键长从2.5148(15)到Br3和Br4原子有对称的原子，连接两个Cd2和一个Cd1原子形成一个三核的[Cd3Br4]作为第二连接单元SBU，相邻的Cd···Cd的距离为这个连接单元SBU与相邻的四个连接单元SBU通过四个配体HPyBIE以二齿侨联模式形成了二维网状结构沿着bc方向。
该配合物经元素分析C30H38Cd3Br6N6O6(1395.32):理论值：C,25.82,H,2.75,N,6.02.实验值:C,25.77,H,2.68,N,6.09％.红外表征(KBr,ν/cm-1):3788w,3435s,3137m,2975m,2927w,1616s,1472s,1461m,1427m,1370w,1306w,1281w,1226w,1119w,1103w,1075w,1041m,1019w,907w,875w,763w,751s,636w,582w,479w。
室温条件下配合物及相应配体的固体荧光发射光谱显示，配体的荧光发射峰位于364nm和445nm(λex＝315nm)，它的荧光来自π*→π或者π*→n的电荷跃迁。配合物{[Cd1.5(μ2-HPyBIE)Br3]·2H2O}n的荧光发射峰为470nm(λex＝298nm)，该荧光峰来自于配体和金属间的荷移跃迁。
本发明涉及一种苯并咪唑衍生物镉配合物的制备方法，包括下述步骤：
(1)将摩尔比为1:1～2的HPyBIE配体和CdBr2分别溶解于乙醇和甲醇溶液中，将二者混合；
(2)室温下搅拌均匀，将溶液置于反应釜中，放于烘箱内，恒温120℃反应72小时，以5℃/h的速度降至室温，有黄色块状晶体析出，过滤，收集产品制成。
本发明的苯并咪唑衍生物镉配合物可以用作荧光光学材料。
本发明涉及的苯并咪唑衍生物镉配合物是用溶剂热法得到，制备方法工艺简单，晶体样品纯度高，生长快，收率高。本发明提供的苯并咪唑类镉配合物是基于苯并咪唑衍生物配体构筑的，室温条件下配合物的固体荧光发射光谱显示，当激发波长为298nm时，配合物可发射波长为470nm。
附图说明
图1是本发明实施例1制备的苯并咪唑类镉配合物的配位模式图；
图2是本发明实施例1制备的苯并咪唑类镉配合物的二维结构图；
图3是本发明实施例1制备的苯并咪唑类镉配合物及配体在298K的固态荧光光谱图。
具体实施方式
实施例1
将3mLCdBr2(0.15mmol)的乙醇溶液加入2mLHPyBIE配体(0.1mmol)的乙醇溶液中，再将该混合溶液放入反应釜中，置于烘箱内，恒温后120摄氏度反应72小时，以5℃/h的速度降至室温，有黄色块状晶体析出，过滤，收集产品，产率：45％。
苯并咪唑衍生物镉配合物的结构测定：
晶体结构测定采用Bruker型X-射线单晶衍射仪，使用经过石墨单色化的Mo-Kα射线 为入射辐射，以扫描方式收集衍射点，经过最小二乘法修正得到晶胞参数，从差值Fourier电子密度图利用SHELXL-97直接法解得晶体结构，并经Lorentz和极化效应修正。详细的晶体测定数据见表1。结构见图1和图2。
表1配合物的晶体学数据
苯并咪唑衍生物镉配合物的发光性质：
我们在室温下测定了配体和配合物的固体荧光光谱(图3)。配体的荧光发射峰位于364nm和445nm(λex＝315nm)，它的荧光来自π*→π或者π*→n的电荷跃迁。配合物{[Cd1.5(μ2-HPyBIE)Br3]·2H2O}n的荧光发射峰为470nm(λex＝298nm)，该荧光峰来自于配体和金属间的荷移跃迁。
Claims (3)
1.一种具有荧光性的苯并咪唑类镉配合物，其特征在于，所述具有荧光性能的苯并咪唑类镉配合物的化学式为：{[Cd1.5(μ2-HPyBIE)Br3]·2H2O}n，式中HPyBIE代表1-(1-(4-吡啶基甲基)-1H-苯并咪唑－2－基)乙醇，n代表重复单元数，该配合物的晶体属于单斜晶系，空间群为P21/c，晶胞参数：α＝γ＝90°，β＝116.212(8)°
2.权利要求1所述具有荧光性的苯并咪唑类镉配合物的制备方法，其特征在于包括如下步骤：
(1)将摩尔比为1:1～2的HPyBIE配体和CdBr2分别溶解于乙醇和甲醇溶液中，将二者混合；
(2)室温下搅拌均匀，将溶液置于反应釜中，放于烘箱内，恒温120℃反应72小时，以5℃/h的速度降至室温，有黄色块状晶体析出，过滤，收集产品制成。
3.权利要求1所述具有荧光性的苯并咪唑类镉配合物的应用，其特征在于用作荧光光学材料。
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| CN114685807A (zh) * | 2022-04-21 | 2022-07-01 | 东南大学 | 一种基于吡唑羧酸类配体的镉配位聚合物及其制法 |
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| CN107793440A (zh) * | 2017-11-23 | 2018-03-13 | 秦皇岛天大环保研究院有限公司 | 荧光性多孔材料、合成方法及其应用 |
| CN114685807A (zh) * | 2022-04-21 | 2022-07-01 | 东南大学 | 一种基于吡唑羧酸类配体的镉配位聚合物及其制法 |
| CN114685807B (zh) * | 2022-04-21 | 2023-03-14 | 东南大学 | 一种基于吡唑羧酸类配体的镉配位聚合物及其制法 |
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