CN105713021A - 一种甲基取代苯并噁唑基吡啶亚铜配合物黄绿色磷光材料 - Google Patents
一种甲基取代苯并噁唑基吡啶亚铜配合物黄绿色磷光材料 Download PDFInfo
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- -1 Methyl-substituted benzoxazolyl pyridine Chemical class 0.000 title description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 31
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Abstract
本发明公开了一种黄绿色磷光亚铜配合物发光材料及其制备方法。本发明的磷光配合物,由一价铜盐与配体络合得到,其分子结构为[Cu(5Me2PBO)(mTol3P)]PF6,式中5Me2PBO和mTol3P分别为电中性配体5甲基2(2苯并恶唑)吡啶和三(间甲苯基)膦。所述配合物既具备小分子易提纯和发光效率高的优点,而且具有高的热稳定性。该材料是由Cu(CH3CN)4PF6与配体的二氯甲烷溶液直接混合反应得到,具有工艺简便、设备简单、原料易得且成本低等优点。该材料可作为光致发光黄绿光材料,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,特别是涉及有机电致发光材料领域。
背景技术
发光材料包括光致发光和电致发光两大类应用领域。光致发光是指物体受到外界光源的照射,从而获得能量产生激发并最终导至发光的现象。紫外辐射、可见光及红外辐射等均可引起光致发光。光致发光材料可用于荧光分析、交通标志、跟踪监测、农用光转换膜、核探测技术中的闪烁体、太阳能转换技术中的荧光集光器等方面。电致发光(electroluminescent,简称EL),是指发光材料在电场作用下,受到电流和电场的激发而发光的现象,是一种将电能直接转换为光能的发光过程。具有这种性能的材料,可制作成电控发光器件,例如发光二极管(LED)和有机发光二极管(Organic Light-Emitting Diode,简称OLED)。而LED和OLED两大类产品,在先进的平板显示和固态节能照明领域都具有非常诱人的应用前景,并且目前已经显示出了其良好的产业化发展势头。由于OLED具有节能、轻薄、无眩光、无紫外线、无红外线、驱动电压低、响应时间短、低温特性好、发光效率高、制造工艺简单、全固态抗震性好、几乎没有可视角度的问题、能够在不同材质的基板上制造、可做成能弯曲的产品等众多优点,近年来备受科技界和产业界的瞩目。而随着社会的发展,OLED技术已在(或将在)彩电、手机、各种显示器、各种照明用或装饰用灯具、飞机等军事装备的显示终端等领域得到越来越广泛的使用。
在OLED器件研究中,提高器件效率是关键技术之一。但在电致发光过程中,空穴和电子复合后,单重态和三重态激子同时产生,按照自旋统计原则,三重态和单重态激子数之比是3∶1,由于三重态激子的辐射跃迁是禁阻的,大部分有机材料的三重态激子发光效率很低,所以有机电致发光器件的最高效率不能超过25%。为使三重态能量得到有效利用,磷光材料的开发成为当前研究的热点。金属机化合物或配合物介于有机物与无机物之间,既有有机物的高荧光量子效率,又有无机物的稳定性,因此被认为是最有发展前景的发光材料。含有重原子(Ir,Pt,Os,Au)的金属有机发光材料由于强烈的自旋-轨道耦合作用,一般具有长寿命的磷光。相对而言,纯有机分子在室温下磷光很弱,甚至根本不能检测出磷光发射。因此基于配合物小分子材料能够方便地实现磷光发射,而且可以实现高效率的发光,也易于制备和纯化、易于制作成薄膜,顺理成章地成为了目前唯一一类实际用于OLED产品发光层的磷光材料。
目前在售的OLED用黄/绿色磷光材料都是贵金属铱和铂等的配合物,虽然它们在性能上已有较好的表现,但是其昂贵的价格也影响到OLED最终产品的推广应用和市场表现。因此针对贱金属Cu(I)配合物磷光材料的研发日益受到关注,Cu(I)配合物很廉价、无环境风险,显然,研究和开发新型的性能优良的Cu(I)配合物发光材料,具有重大的意义和很好的市场应用前景。而用Cu(I)配合物作为黄/绿色磷光材料则由来已久(N.Armaroli,G.Accorsi,F.Cardinali,A.Listorti,Top.Curr.Chem.2007,280,69-115.),这种廉价的Cu(I)配合物发光材料可由Cu(I)离子和合适的有机配体方便地制备,只是在OLED工作温度范围其发光强度尚达不到应用需求。因此开发新型廉价的Cu(I)配合物黄/绿色磷光材料具有重大的实际应用价值。
发明内容
本发明内容的目的是提供一种黄绿色磷光亚铜配合物发光材料及其制备方法。通过亚铜盐与有机配体的溶液发生配位反应,方便且廉价地制备获得了发光性能和热稳定性能良好的亚铜配合物发光材料,其黄绿色磷光发光强度很大、热稳定性也好,而且其发光衰减特性非常符合OLED器件对材料磷光发光寿命的要求,将其应用于OLED发光层材料有利于产品成本的降低。
本发明的技术方案之一,是提供一种新的黄绿色磷光亚铜配合物发光材料,由Cu(CH3CN)4PF6与配体发生配位反应得到,其分子结构为[Cu(5-Me-2-PBO)(m-Tol3P)]PF6,式中m-Tol3P为电中性双膦配体三-(间甲苯基)膦,5-Me-2-PBO为电中性杂环配体5-甲基-2-(2-苯并噁唑)吡啶。
所述配体5-甲基-2-(2-苯并噁唑)吡啶,是甲基取代的苯并噁唑和吡啶的结合体,其分子结构如式(I):
所述配体中苯并噁唑结构中的O未参与配位,而其N原子与吡啶结构中的N原子与亚铜离子形成双齿螯合配位。
所述发光材料发光材料为单斜晶系,P21/c空间群,晶胞参数为 α=90°,β=95.122(4)°,γ=90°,Z=1,DC=1.621g/cm3,晶体颜色为黄绿色;该发光材料结构表现为离子型配合物,其中六氟磷酸根为抗衡阴离子,而阳离子由亚铜离子和m-Tol3P、5-Me-2-PBO络合形成的配位阳离子,该配位阳离子中亚铜离子采用CuN2P2四面体型配位模式,式中两个N分别来自于一个双齿螯合配体5-Me-2-PBO中的苯并恶唑基团和吡啶基团,两个P来自于另外两个端基膦配体;其分子结构如式(II):
所述发光材料应用于黄绿色磷光材料,该材料收到很宽波长范围(300-500nm)的紫外光或可见光的激发,都能发出很强的黄绿光,其最大发光波长为560nm,色坐标为(0.4564,0.5253),发光寿命为7.4微秒。
本发明的技术方案之二,是提供一种黄绿色磷光亚铜配合物发光材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6的制备方法。该制备方法是由Cu(CH3CN)4PF6与配体5-Me-2-PBO和m-Tol3P的二氯甲烷溶液分步混合发生配位反应,最后旋蒸产生晶体粉末的产物而实现。其具体实施方案分为五步骤:
(1)室温下将Cu(CH3CN)4PF6粉末溶解在二氯甲烷中;
(2)室温下将三-(间甲苯基)膦粉末溶解在二氯甲烷中;
(3)将所述述两种溶液混合,并搅拌使之充分反应,得到澄清溶液A;
(4)室温下将5-Me-2-PBO粉末溶解在二氯甲烷中,再加入溶液A中混合搅拌,使之充分发生配位反应得溶液B;
(5)在溶液B中加入异丙醇,在室温下进行减压蒸发,真空干燥,得到黄色晶体产物。
本发明的制备方法中,所述三种反应物的摩尔比Cu(CH3CN)4PF6∶m-Tol3P∶5-Me-2-PBO为1∶2∶1。
本发明的有益效果,首先是所提供的黄绿色磷光亚铜配合物发光材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6,其中引入的苯并噁唑基团有利于分子激发态发光,金属Cu到配体的电荷跃迁(MLCT)的存在有效促进系间窜越,而取代基甲基等的存在,造成Cu(I)周围配体存在有效空间位阻,可抑制分子激发态的非辐射衰减,配体5-Me-2-PBO和m-Tol3P都为多芳环的配体,都具有很大的刚性特征,因而该分子材料具有好的磷光发射性能。该配合物材料既具备廉价和易于纯化的优点,而且具有很好的溶解性和热稳定性,为发光材料的进一步应用提供了技术支持。
本发明的有益效果,其次是制备黄绿色磷光亚铜配合物发光材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6的方法,具有工艺简便,所用设备简单,生产成本低,可以在很短的时间内得到具有很高产率的产物等优点。
附图说明
图1.黄绿色磷光亚铜配合物发光材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6分子的单晶结构图。
图2.黄绿色磷光亚铜配合物发光材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6分子在单胞内及其周边空间的堆积图。
图3.黄绿色磷光亚铜配合物发光材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6的X-射线粉末衍射图谱:(a)为根据实施例2中单晶结构数据计算获得的谱图;(b)为本发明实施例1中所得粉末的图谱。
图4.黄绿色磷光亚铜配合物发光材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6的紫外-可见吸收(UV-Vis)光谱图。
图5.黄绿色磷光亚铜配合物发光材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6样品在560纳米监控波长下测定的激发谱图。
图6.黄绿色磷光亚铜配合物发光材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6样品在420纳米波长光激发下测定的光发射谱图。
具体实施方式
本发明的实现过程和材料的性能由实施例说明:
实施例1
大量的亚铜配合物[Cu(5-Me-2-PBO)(m-Tol3P)]PF6晶体样品的制备:称取0.1mmol(37.3mg)的[Cu(CH3CN)4]PF6溶于5mL CH2Cl2中,再依次称取0.2mmol(61mg)的m-Tol3P和0.1mmol(21.3mg)的4-Me-2-PBO,分别溶于3mL CH2Cl2中;将三种溶液依次混合(所述三种反应物的摩尔比Cu(CH3CN)4PF6∶m-Tol3P∶5-Me-2-PBO为1∶2∶1),并搅拌使之充分发生配位反应,最后将所得黄色溶液过滤,加入少量异丙醇后在室温下减压蒸发,得到大量黄色晶体产物,真空干燥,产率92%(以Cu计)。
实施例2
合成黄绿色磷光配合物材料[Cu(5-Me-2-PBO)(m-Tol3P)]PF6的单晶:称取0.1mmolCu(CH3CN)4PF6和0.2mmol的m-Tol3P配体溶解在3mL二氯甲烷中后,再将3mL含0.1mmol的4-Me-2-PBO配体的二氯甲烷溶液一次加入上述溶液中,搅拌使之完全溶解后过滤,在滤液上覆盖异丙醇促使产物结晶,静置数天后析出大量黄色条棒状晶体。挑选一颗0.42mm×0.40mm×0.36mm尺寸的黄色晶体用于X-射线单晶结构测试。该化合物的分子结构图示于附图1,其晶胞堆积结构图示于附图2。
对配合物[Cu(5-Me-2-PBO)(m-Tol3P)]PF6的纯相晶体样品进行了一系列性能测试。对本发明材料晶体进行了稳态荧光测试,结果表明该材料在不同的激发波长作用下,都能发射出强烈的黄绿色光,色坐标值为(0.4564,0.5253),具体的激发光谱和发射光谱如附图5和图6所示。而对该材料的瞬态荧光测试表明,其发光寿命为7.4微秒,属于磷光发射。可见,该材料可应用于多种波长激发的黄绿色磷光材料,也非常适合用于OLED发光层的黄绿色磷光材料。
Claims (4)
1.一种基于甲基取代苯并噁唑基吡啶的亚铜配合物黄绿色磷光材料,其特征在于:发光材料的结构式为[Cu(5-Me-2-PBO)(m-Tol3P)]PF6,式中m-Tol3P为电中性膦配体三-(间甲苯基)膦;式中5-Me-2-PBO为中性杂环配体5-甲基-2-(2-苯并噁唑)吡啶,该配体是甲基取代的苯并噁唑和吡啶的结合体,其分子结构如式(I):
室温下该配合物发光材料为单斜晶系,P21/c空间群,晶胞参数为 α=90°,β=95.122(4)°,γ=90°,Z=1,DC=1.621g/cm3,晶体颜色为黄绿色;该发光材料结构表现为离子型配合物,其中六氟磷酸根为抗衡阴离子,而阳离子由亚铜离子和m-Tol3P、5-Me-2-PBO络合形成的配位阳离子,该配位阳离子中亚铜离子采用CuN2P2四面体型配位模式,式中两个N分别来自于一个双齿螯合配体5-Me-2-PBO中的苯并恶唑基团和吡啶基团,两个P来自于另外两个端基膦配体;其分子结构如式(II):
2.根据权利要求1所述亚铜配合物黄绿色磷光材料的制备方法,该方法包括以下步骤:
(1)室温下将Cu(CH3CN)4PF6粉末溶解在二氯甲烷中;
(2)室温下将三-(间甲苯基)膦粉末溶解在二氯甲烷中;
(3)将所述述两种溶液混合,并搅拌使之充分反应,得到澄清溶液A;
(4)室温下将5-Me-2-PBO粉末溶解在二氯甲烷中,再加入溶液A中混合搅拌,使之充分发生配位反应得溶液B;
(5)在溶液B中加入异丙醇,在室温下进行减压蒸发,真空干燥,得到黄色晶体产物。
3.根据权利要求2所述亚铜配合物黄绿色磷光材料的制备方法,其特征在于:所述三种反应物的摩尔比Cu(CH3CN)4PF6∶m-Tol3P∶5-Me-2-PBO为1∶2∶1。
4.根据权利要求1所述亚铜配合物黄绿色磷光材料的应用,其特征在于所述发光材料在560nm处有最大发射峰,可作为光致发光材料,或用作多层电致发光器件中的发光层发光材料。
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