CN108424765B - 一种黄色磷光Cu(I)配合物发光材料及其制备方法 - Google Patents
一种黄色磷光Cu(I)配合物发光材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种黄色磷光Cu(I)配合物发光材料及其制备方法，所述的磷光Cu(I)配合物由一价铜盐与配体络合得到，其分子结构为Cu(2‑OFPI)(POP)(PF6)，式中POP和2‑OFPI为电中性配体双(2‑苯基磷苯基)醚和1‑(9H‑芴‑2基)‑2‑[(2‑吡啶‑2基)‑1H‑咪唑‑1‑基]乙酮，所述配合物具有发光效率高和发光寿命长的优点，而且具有小分子易提纯，稳定性强易溶解的优点，该材料是由Cu(CH3CN4)PF6与配体的二氯甲烷溶液直接混合反应得到，具有结构简单、工艺简便、设备简单、原料充足且成本低廉等优点，该材料可作为光致发光黄光材料，也可用作多层有机材料组成的电致发光器件中的发光层磷光材料。
Description
技术领域
本发明涉及发光材料技术领域，涉及光致发光材料领域和电致发光材料领域，主要涉及一价铜配合物及其制备方法和应用。
背景技术
磷光材料的研究和开发对象，一般都是金属-有机配合物小分子材料而不是有机小分子，原因在于纯有机分子在室温下磷光很弱，甚至不能检测出磷光发射。而配合物小分子材料能够方便的实现磷光发射。有机过渡金属配合物，由于金属重原子诱导的自旋耦合作用(SOC)较强，如钌(Ru)、锇(Os)、铱(Ir)，可俘获单态和三态的光子参与发光，理论上可获得高的内在发光效率(近100％)和长的激发态寿命(毫秒级)，在太阳能电池转换、离子检测、生物探针、发光二极管等领域有着非常广阔的应用。而贵金属在地球上的含量较少，毒性大，无法大规模的使用。为了解决这些潜在问题，科学家们通过研究发现，位于第一主族的铜离子所形成的铜配合物，有着和其他贵金属配合物相似的光化学和光物理特性，有可能替代上述贵金属配合物，成为新一代发光功能新材料。而且铜配合物具有其他贵金属配合物无法取代的优点：成本低、易开采、毒性低、污染小，更能和配体形成多种配位方式，发生多种电子跃迁等。虽然铜配合物具有众多的优点，但自身也存在一些缺陷。相比较贵金属，铜配合物一般具有较短的激发态寿命(纳秒级别)，Cu(I)配合物发光多以绿光和蓝光为主、发光亮度普遍不高等。我们试着引入一些特定的官能团来提升Cu(I)配合物的发光亮度和效率，而用Cu(I)配合物作为黄色磷光材料可由Cu(I)离子和有机配体方便的制备，因此开发新型廉价的Cu(I)配合物材料具有重大的实际应用价值。
发明内容
本发明目的是提供一种新的黄色磷光Cu(I)配合物的发光材料及其制备方法，通过Cu(I)离子与有机配体溶液配位反应，简便廉价的制备了发光性能和热稳定性良好的Cu(I)配合物发光材料，由于芴及其衍生物在可见光区域表现出良好的吸光能力，当将其引入到配合物体系中，能够改善配合物的光学特性，因此我们在配体上成功的引入有机发色团芴，其Cu(I)配合物磷光发光强度大、发光衰减特征与OLED器件对材料磷光发光寿命的要求相符合，将其应用于太阳能电池发光材料有利于降低产品成本。
一种黄色磷光Cu(I)配合物发光材料及其制备方法：发光材料的结构式为Cu(2-OFPI)(POP)(PF6)，式中POP为电中性含P配体双(2-二苯基磷苯基)醚，式中2-OFPI为电中性杂环配体1-(9H-芴-2基)-2-[(2-吡啶-2基)-1H-咪唑-1-基]乙酮，所述配体为吡啶基咪唑和乙酰基芴的结合体，其分子结构为：
所述配合物发光材料为离子型配合物，配合物分子中的六氟磷酸根为抗衡阴离子，配位阳离子为亚铜离子和配体POP、2-OFPI络合形成；所述配位阳离子中Cu(I)采用CuN2P2四面体配位模式，其中两个N分别来自于一个双齿螯合的吡啶基团和芴基咪唑基团，两个P来自于另一个双齿螯合的POP配体，其分子结构为：
所述的一种黄色磷光Cu(I)配合物发光材料及其制备方法：具体制备方法包括以下步骤：
(1)反应温度0～100℃下，将Cu(CH3CN4)PF6粉末溶于二氯甲烷溶液；
(2)反应温度0～100℃下，将配体POP和2-OFPI的粉末溶于二氯甲烷溶液；
(3)将上述步骤制得的两种二氯甲烷溶液混合，并充分搅拌1～3h，使之发生配位反应；
(4)将反应液过滤，并将所得滤液在真空下旋蒸，除去溶剂即得到黄色固体产物。
所述的一种黄色磷光Cu(I)配合物发光材料及其制备方法：步骤(1)(2)中三种反应物的摩尔比Cu(CH3CN4)PF6：2-OFPI：POP为1:1:1。
一种黄色磷光Cu(I)配合物发光材料及其制备方法：所制得的发光材料应用于黄光光致发光材料。
一种黄色磷光Cu(I)配合物发光材料及其制备方法：所制得发光材料用作多层有机材料组成的电致发光器件中的发光层磷光材料。
本发明的有益效果
1、本发明的有益效果之一是成功的将有机荧光基团芴引入到了2-吡啶基咪唑上形成新的配体L1即2-OFPI，并成功合成了Cu(I)配合物Cu(2-OFPI)(POP)(PF6)，同时对其光学性质进行了测试分析。由于N-H键的振动频率相对C-H键较弱，随着配体钟N原子的增加，降低了振动所引起的发光淬灭，提高了配合物的荧光量子产率及激发态寿命。
2、本发明的有益效果之二是在咪唑环上引入有机荧光基团芴后，能够增加金属铜到配体L2的MLCT跃迁几率,同时配合物本身具有的空间位阻抑制了分子激发态的非辐射衰减，提高了可见光区的吸光能力，并且进一步的提高了激发态的寿命。
3、本发明的有益结果之三是制备黄色磷光Cu(I)配合物Cu(2-OFPI)(POP)(PF6)的方法，其具体工艺简单、设备简单、原料易得、生产成本低等优点，并且该配合物材料易于纯化、有很好的溶解性和热稳定性。
附图说明
图1为配体L1(2-OFPI)的合成路线图；
图2为配体L1(2-OFPI)的紫外-可见吸收(UV-Vis)光谱图；
图3为磷光配合物Cu(2-OFPI)(POP)(PF6)的合成路线图；
图4为磷光配合物Cu(2-OFPI)(POP)(PF6)的紫外-可见吸收(UV-Vis)光谱图；
图5为磷光配合物Cu(2-OFPI)(POP)(PF6)在350纳米激发波长下的光发射谱图。
具体实施方式
实施例1
配体L1(2-OFPI)的合成。
如说明书附图1合成路线所示：
(1)合成配体L1(2-OFPI)前驱M1(2-溴-1-(9H-芴-2-基)乙酮)，结构式为：(III)
在50mL的圆底烧瓶中加入溴化铜(2.68g,12mmol)和25mL的乙酸乙酯，将上述混合物转移至油浴锅中，搅拌回流，将2-乙酰基芴(1.25g,6mmol)溶解在13mL的二氯甲烷溶液中，缓慢滴加到上述溶液中，15min内滴加完毕，搅拌回流3.5h后，趁热经硅藻土过滤，用乙酸乙酯洗涤几次，滤液通过减压旋转蒸发除去溶剂，得到灰绿色固体。
(2)合成配体L1(2-OFPI)前驱M2(2-(2-吡啶基)咪唑)，结构式为：(VI)
(3)合成配体L1(2-OFPI)：
氮气环境下，在25mL的圆底烧瓶中加入40％的氢化钠(0.2g,3.0mmol)和9mL干燥的DMF，将2-(2-吡啶基)咪唑(0.29g,2mmol)溶解在4mL干燥的DMF中，缓慢滴加到上述溶液中，室温搅拌30min后，将2溴-1-(9H-芴-2-基)乙酮(0.57g,2mmol)和4mL干燥的DMF的混合溶液加入到反应体系中，室温下反应过夜，向体系中缓慢加入水除去未反应的氢化钠，乙酸乙酯萃取，有机相分别用水和饱和氯化钠溶液洗涤几次，用无水硫酸镁干燥，过滤旋转蒸发除去溶剂得到粗产物，通过硅胶柱层析分离，(洗脱溶剂为乙酸乙酯)得到纯净的目标产物0.20g，测得为产率20％，1H NMR(400MHz,DMSO):δ＝8.27(s,1H),8.09(dd,J＝26.1,6.9Hz,5H),7.83(t,J＝7.2Hz,1H),7.68(d,J＝6.8Hz,1H),7.43(dd,J＝24.2,17.1Hz,3H),7.20(s,1H),7.12(s,1H),6.22(s,2H),4.05(d,J＝12.7Hz,2H).MS:m/z＝351(M+)。
实施例2
磷光配合物Cu(2-OFPI)(POP)(PF6)的合成：如说明书附图3合成路线所示，在50mL的圆底烧瓶中依次加入六氟磷酸四乙腈铜{[Cu(CH3CN)4](PF6)(0.062g,0.2mmol)}、POP(0.108g,0.2mmol)和二氯甲烷溶液(10mL)，氮气保护下室温搅拌2h，再将0.2mmol的配体L1(2-OFPI)溶解在经过脱气处理的二氯甲烷溶液中，注入到上述混合溶液中，室温反应2h，将反应后的溶液经过硅藻土过滤，滤液减压旋转蒸发除去溶剂得到固体粉末，将粉末用少量的二氯甲烷溶液溶解，加入少量的乙腈和大量的乙醚，观察到有大量的沉淀产生，过滤收集沉淀，沉淀用乙醚洗涤几次后干燥得到产物，收率:43％(82mg)，1H NMR(400MHz,DMSO):δ＝8.35(s,1H),8.15(d,J＝35.9Hz,4H),7.89(s,2H),7.70(d,J＝6.1Hz,2H),7.62-7.01(m,30H),6.56(d,J＝42.5Hz,4H),4.09(s,2H).MS:m/z＝939(M+)。
测定制得的磷光配合物Cu(2-OFPI)(POP)(PF6)光物理性质：室温下配合物Cu(2-OFPI)(POP)(PF6)在浓度为1×10-5mol/L溶液中的紫外可见吸收峰在350-450nm范围内，如说明书附图4所示，这是配合物中心原子Cu(I)到配体分子电子跃迁引起的，室温下10％配合物Cu(2-OFPI)(POP)(PF6)掺杂在PMMA中的发射峰在574nm。发射光谱如说明书附图5所示，发光量子产率为25.1％，发光寿命为28.0微秒(μs)，由此可以得出本发明制得的磷光配合物Cu(2-OFPI)(POP)(PF6)的磷光发光量子产率25.1％处于较高水平、发光寿命复合要求。
Claims (5)
1.一种黄色磷光Cu(I)配合物发光材料，其特征在于：所述发光材料的结构式为Cu(2-OFPI)(POP)(PF6)，式中POP为电中性含P配体双(2-二苯基磷苯基)醚，式中2-OFPI为电中性杂环配体1-(9H-芴-2基)-2-[(2-吡啶-2基)-1H-咪唑-1-基]乙酮，所述配体为吡啶基咪唑和乙酰基芴的结合体，其分子结构为：
所述配合物发光材料为离子型配合物，配合物分子中的六氟磷酸根为抗衡阴离子，配位阳离子为亚铜离子和配体POP、2-OFPI络合形成；所述配位阳离子中Cu(I)采用CuN2P2四面体配位模式，其中两个N分别来自于一个双齿螯合的吡啶基团和芴基咪唑基团，两个P来自于另一个双齿螯合的POP配体，其分子结构为：
2.根据权利要求1所述的一种黄色磷光Cu(I)配合物发光材料，其特征在于：具体制备方法包括以下步骤：
(1)反应温度0～100℃下，将Cu(CH3CN4)PF6粉末溶于二氯甲烷溶液；
(2)反应温度0～100℃下，将配体POP和2-OFPI的粉末溶于二氯甲烷溶液；
(3)将上述步骤制得的两种二氯甲烷溶液混合，并充分搅拌1～3h，使之发生配位反应；
(4)将反应液过滤，并将所得滤液在真空下旋蒸，除去溶剂即得到黄色固体产物。
3.根据权利要求2所述的一种黄色磷光Cu(I)配合物发光材料的制备方法，其特征在于：步骤(1)(2)中三种反应物的摩尔比Cu(CH3CN4)PF6：2-OFPI：POP为1:1:1。
4.根据权利要求1所述的一种黄色磷光Cu(I)配合物发光材料，其特征在于：所制得的发光材料应用于黄光光致发光材料。
5.根据权利要求1所述的一种黄色磷光Cu(I)配合物发光材料，其特征在于：所制得发光材料用作多层有机材料组成的电致发光器件中的发光层磷光材料。
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