CN110845521A - 一种磁性荧光配合物及其制备方法和应用 - Google Patents
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- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000010668 complexation reaction Methods 0.000 title description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 39
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 26
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
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- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- VEEIYHUOLCUPSA-UHFFFAOYSA-M sodium;iodide;dihydrate Chemical compound O.O.[Na+].[I-] VEEIYHUOLCUPSA-UHFFFAOYSA-M 0.000 claims description 8
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- YXGZTNUNHBXFAX-UHFFFAOYSA-N copper;1,10-phenanthroline Chemical compound [Cu+2].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YXGZTNUNHBXFAX-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域
本发明涉及配合物制备技术领域,具体涉及的是一种磁性荧光配合物及其制备方法和应用。
背景技术
配合物具有丰富的光、电、磁等性能而有着巨大的应用前景。比如荧光配合物可用于荧光发光器、荧光传感器和荧光免疫分析等领域;磁性配合物可作为信息存储器、磁制冷和量子计算设备的潜在应用材料。随着社会的发展,具有多功能的配合物越来越受欢迎。比如同时具有磁性和荧光的双功能配合物,它可应用于磁光传感器等领域。
配合物产生荧光是因为其受光照射后,光的能量能使一些电子由基态跃迁到第一激发单线态或第二激发单线态等;电子处于第一激发单线态或第二激发单线态等时是不稳定的,所以会跃迁返回到基态。当电子由第一激发单线态跃迁返回到基态时,能量会以光的形式释放,所以产生荧光。而当荧光配合物中存在磁性金属离子时,如Ni2+,Co2+和Cu2+等,这些金属离子的d轨道处于未饱和状态,常会诱导电子转移,从而导致荧光猝灭。因此,设计合成具有荧光和磁性的双功能配合物具有很大的意义,但同时又存在较大的挑战。
发明内容
本发明的目的在于提供一种磁性荧光配合物,在配合物中存在Cu2+磁性金属离子,荧光并未猝灭,此配合物具有反铁磁性且能产生高强度的荧光。
本发明的目的还在于提供一种磁性荧光配合物的制备方法,配体原料成本低,制备方法简易,且产率高。
本发明的目的又在于提供一种磁性荧光配合物的应用。
为了达成上述目的,本发明的解决方案是:
一种磁性荧光配合物的制备方法,是先在室温下,将三水合硝酸铜、邻菲罗啉和二水合碘化钠加入到去离子水中,搅拌混合均匀,然后密封加热到120~200℃进行反应,保温12~96h,再冷却到室温,最后将反应生产的沉淀用水洗涤多次后,得到所述磁性荧光配合物。
所述三水合硝酸铜、邻菲罗啉和二水合碘化钠的摩尔比为1∶2~4∶4~8。
所述三水合硝酸铜的摩尔用量和所述去离子水的体积比为1mol∶20~28mL。
一种磁性荧光配合物用于制作荧光发光器件、信息存储器件或者磁光传感器件。
采用上述技术方案后,本发明一种磁性荧光配合物,在配合物中存在Cu2+磁性金属离子,荧光并未猝灭,此配合物具有反铁磁性且能产生高强度的荧光。本发明一种磁性荧光配合物的制备方法,配体原料成本低,制备方法简易,且产率高。
附图说明
图1为[CuI(phen)2]2Cu(phen)2I3的结构图;
图2为[CuI(phen)2]2Cu(phen)2I3中阳离子间形成π···π堆积作用的示意图;
图3为[CuI(phen)2]2Cu(phen)2I3的粉末X射线衍射(PXRD)图谱与单晶衍射数据模拟的PXRD图谱的比较图;
图4为[CuI(phen)2]2Cu(phen)2I3的热重分析图;
图5为[CuI(phen)2]2Cu(phen)2I3在340nm激发波长下的发射光谱;
图6为[CuI(phen)2]2Cu(phen)2I3的磁性分析图。
具体实施方式
为了进一步解释本发明的技术方案,下面通过具体实施例来对本发明进行详细阐述。
实施例1
1、制备:
一种磁性荧光配合物的制备方法:先在室温下,将121mg三水合硝酸铜(0.5mmol)、180mg邻菲罗啉(1mmol)、558mg二水合碘化钠(3mmol)和10mL去离子水加入到20mL高压釜中,并搅拌混合均匀成混合溶液。然后将该混合溶液密封加热到180℃进行反应,保温36h,再冷却到室温,最后将反应生成的沉淀用水洗涤多次后,得到黑色片状晶体,即得该磁性荧光配合物。根据使用的三水合硝酸铜用量计算得到产物的产率为57.3%。
2、结构表征:
通过单晶X射线衍射实验得到本发明的磁性荧光配合物的单晶结构。如图1所示,制备得到的磁性荧光配合物的化学式为[CuI(phen)2]2Cu(phen)2I3,其中phen为邻菲罗啉。该配合物属于单斜晶系,空间群为P21/c,晶胞参数为 β=108.381(7)°,单胞体积此配合物的不对称单元由两个[CuI(phen)2]+阳离子、一个[Cu(phen)2]+阳离子和三个I-阴离子组成。该配合物的结构中,[Cu(phen)2]+阳离子中的Cu1为+1价,[CuI(phen)2]+阳离子中的Cu2和Cu3均为+2价。如图2所示,阳离子间的π···π堆积作用导致形成二维阳离子层,I-阴离子位于阳离子层间。
3、性能测试:
如图3所示,制备得到的该磁性荧光配合物的PXRD图谱与单晶衍射数据模拟的PXRD图谱相吻合,说明产物为纯相。
通过热重分析(如图4)证明该磁性荧光配合物可在温度25~200℃范围内保持稳定,具有在较宽温度范围内应用的价值。
通过荧光光谱分析,如图5所示,该磁性荧光配合物在340nm的紫外光照射下产生高强度的蓝色荧光(波长范围为410~440nm)。
通过测该磁性荧光配合物的变温磁化率(χ),得到有效磁矩(μeff)和摩尔磁化率倒数(1/χM)与温度的关系图,如图6所示,在300K时,有效磁矩为1.93B.M.,对应一个未耦合的Cu2+离子;当温度降低到30K时,有效磁矩缓慢降低到1.41B.M.;当温度继续降低到2.0K时,有效磁矩快速降低到1.06B.M.。该有效磁矩随温度变化趋势表明此磁性荧光配合物存在反铁磁耦合作用。在60~300K温度范围内,应用居里-外斯定律对1/χM~T曲线进行拟合,得到外斯温度为-43.26K。外斯温度为负值,也说明该磁性荧光配合物具有反铁磁性。结合该磁性荧光配合物的结构,反铁磁作用的产生应归因于[CuI(phen)2]+阳离子间的π···π堆积作用。
4、应用
该磁性荧光配合物用于制作荧光发光器件、信息存储器件或者磁光传感器件。
实施例2
一种磁性荧光配合物的制备方法:先在室温下,将121mg三水合硝酸铜(0.5mmol)、360mg邻菲罗啉(2mmol)、372mg二水合碘化钠(2mmol)和12mL去离子水加入到20mL高压釜中,并搅拌混合均匀成混合溶液。然后将该混合溶液密封加热到140℃进行反应,保温72h,再冷却到室温,最后将反应生成的沉淀用水洗涤多次后,得到黑色片状晶体,即得该磁性荧光配合物。根据使用的三水合硝酸铜用量计算得到产物的产率为59.2%。
实施例3
一种磁性荧光配合物的制备方法:先在室温下,将121mg三水合硝酸铜(0.5mmol)、270mg邻菲罗啉(1.5mmol)、744mg二水合碘化钠(4mmol)和14mL去离子水加入到20mL高压釜中,并搅拌混合均匀成混合溶液。然后将该混合溶液密封加热到120℃进行反应,保温96h,再冷却到室温,最后将反应生成的沉淀用水洗涤多次后,得到黑色片状晶体,即得该磁性荧光配合物。根据使用的三水合硝酸铜用量计算得到产物的产率为53.5%。
实施例4
一种磁性荧光配合物的制备方法:先在室温下,将121mg三水合硝酸铜(0.5mmol)、180mg邻菲罗啉(1mmol)、372mg二水合碘化钠(2mmol)和12mL去离子水加入到20mL高压釜中,并搅拌混合均匀成混合溶液。然后将该混合溶液密封加热到200℃进行反应,保温12h,再冷却到室温,最后将反应生成的沉淀用水洗涤多次后,得到黑色片状晶体,即得该磁性荧光配合物。根据使用的三水合硝酸铜用量计算得到产物的产率为52.8%。
上述实施例和图式并非限定本发明的产品形态和式样,任何所属技术领域的普通技术人员对其所做的适当变化或修饰,皆应视为不脱离本发明的专利范畴。
Claims (5)
2.制备如权利要求1所述的一种磁性荧光配合物的制备方法,其特征在于:是先在室温下,将三水合硝酸铜、邻菲罗啉和二水合碘化钠加入到去离子水中,搅拌混合均匀,然后密封加热到120~200℃进行反应,保温12~96h,再冷却到室温,最后将反应生产的沉淀用水洗涤多次后,得到所述磁性荧光配合物。
3.根据权利要求2所述的一种磁性荧光配合物的制备方法,其特征在于:所述三水合硝酸铜、邻菲罗啉和二水合碘化钠的摩尔比为1∶2~4∶4~8。
4.根据权利要求2所述的一种磁性荧光配合物的制备方法,其特征在于:所述三水合硝酸铜的摩尔用量和所述去离子水的体积比为1mol∶20~28mL。
5.一种如权利要求1所述的磁性荧光配合物在制作荧光发光器件、信息存储器件或者磁光传感器件中的应用。
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