CN106008562A - 一种含邻菲罗啉配体的四面体型亚铜配合物发光材料 - Google Patents
一种含邻菲罗啉配体的四面体型亚铜配合物发光材料 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 55
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003446 ligand Substances 0.000 title claims abstract description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 46
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011368 organic material Substances 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 13
- 238000010668 complexation reaction Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
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- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 abstract 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000005424 photoluminescence Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 32
- 238000004020 luminiscence type Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
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- 238000000695 excitation spectrum Methods 0.000 description 2
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- -1 iridium (Ir) Chemical class 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000904 thermoluminescence Methods 0.000 description 1
- 230000001052 transient effect Effects 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
本发明公开了一种绿色磷光四面体型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(Phen)(PPh3)2(PF6),式中Phen和PPh3为电中性配体1,10‑邻菲罗啉和三苯基膦。所述配合物既具备小分子易提纯和发光效率高的优点,而且具有易用有机溶剂溶解的优点。该材料是由Cu(CH3CN)4PF6与两种配体的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
发光材料有光致发光、阴极射线发光、电致发光、热释发光、光释发光、辐射发光等。其中,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,又称电场发光。目前电致发光的研究方向主要为有机材料的应用,例如有机发光二极管(Organic Light-Emitting Diode,简称OLED)。按其发光材料的分子量,OLED可以分为小分子有机发光二极管(OLED或SM-OLED),高分子(又称聚合物)有机发光二极管(PLED或P-OLED)两类,前者分子量在500~2000之间,后者在10000~100000之间。
自1987年Tang等首次报道了高亮度且低工作电压的有机电致发光器件(OLEDs)之后,大家对其有了空前的研究热情。自1997年日本Pioneer公司率先将OLEDs商业化后,因其在固态照明和显示方面的巨大商业价值而被认为是新一代的平板显示技术。OLED作为平板显示技术与现有的液晶显示技术相比,具有更快的响应速度、更低的驱动电压、更广阔的视角等显著特点,可被进一步应用于电视、电脑、仪表等作为显示屏幕。如今,三星、LG、索尼、夏普等众多国际电子大公司纷纷参与到了OLEDs的技术研发之中。
有机电致发光按其发光机理可分为荧光和磷光两类:前者是单重态激子的辐射衰减跃迁,发光寿命为纳秒级的;后者是三重态激子辐射衰减跃迁所致,因其跃迁过程中存在禁阻,故发光寿命为微秒级的。若器件的发光层仅用荧光材料制作则会受其内量子效率(IQE)(理论上只有25%)的限制而不能充分利用能源。而过渡金属如铱(Ir)、钌(Ru)、铼(Re)、铂(Pt)等发光配合物作为一种磷光材料因具有很强的自旋-轨道耦合作用,可以充分利用包括三重态和三重态的所有输入能量,故其内量子效率理论上可达到100%,相比荧光材料高出整整三倍多。国内从事OLED研究的人士则多以铱等贵金属作为磷光体。然而铱等配合物目前存在成本高、资源少以及不环保等不可避免的局限性。因此,研发一些低成本、多资源且环保的磷光材料迫在眉睫。Cu(I)配合物以其绿色环保和价格低廉等优势崭露头角,因其还具有铜资源储量大、结构多样化、光物理性质独特等特点而日益倍受关注。
经多年研究发展,发现Cu(I)配合物在现实运用中还存在着一些不足,如Cu(I)配合物发光颜色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功能的官能团来提升Cu(I)配合物的发光亮度和效率。邻菲罗啉及其衍生物被广泛应用于光电材料等领域,其中1,10-邻菲罗啉易与亚铜离子配位形成稳定的发光配合物,该类配合物具有良好的物理化学性质,故被广泛应用于制备有机电致发光材料。开发新型廉价的Cu(I)配合物绿色磷光材料具有重大的实际应用价值。
发明内容
本发明的目的是提供一种新的绿色磷光四面体型亚铜配合物发光材料及其制备方法。通过Cu(I)离子和有机配体的溶液配位反应,方便且廉价地制备获得了发光性能良好的Cu(I)配合物发光材料,其绿色磷光发光强度很大,而且其发光衰减特征非常符合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,是提供一种新的绿色磷光四面体型亚铜配合物发光材料,由Cu(CH3CN)4PF6与配体进行配位反应得到,其分子结构为Cu(Phen)(PPh3)2(PF6),式中Phen和PPh3分别为电中性配体1,10-邻菲罗啉和三苯基膦。
所述配体1,10-邻菲罗啉,其分子结构如式(I):
所述配体中的N原子与亚铜离子形成一个双齿螯合的配位模式。
所述发光材料为单斜晶系,P21/n空间群,晶胞参数 α=90°,β=92.013(3)°,γ=90°,Z=4,Dc=1.429g/cm3,晶体颜色为浅绿色;配合物表现为离子型配合物,其中的抗衡阴离子为六氟磷酸根,而阳离子则是由亚铜离子和配体Phen、PPh3络合形成的配位阳离子;该配位阳离子中Cu(I)采用CuN2P2四面体配位模式,其中两个N都来自于一个双齿螯合的Phen配体,而两个P来自于两个PPh3配体;其分子结构如式(II):
所述发光材料应用于绿光磷光材料,该材料受到很宽波长范围(300-470nm)的紫外光或可见光的激发,都能发出很强的绿色光,其最大发光波长为510nm,色坐标值为(0.2505,0.5177),发光寿命为4微秒。
所述绿色磷光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。
本发明的技术方案之二,是提供一种绿色磷光四面体型亚铜配合物Cu(Phen)(PPh3)2(PF6)发光材料的制备方法。该制备方法是由Cu(CH3CN)4PF6和两种配体的在溶液中混合发生配位反应,然后将溶剂除去从而析出产物的晶体而实现。其具体实施方案分为四个步骤:
(1)室温下将Cu(CH3CN)4PF6于乙腈和二氯甲烷混合溶剂中完全溶解;
(2)室温下将配体Phen和PPh3的粉末完全溶解于二氯甲烷中;
(3)将所述两种溶液混合,并搅拌使之充分发生配位反应;
(4)将反应液过滤,并加入正己烷后将所得滤液在抽真空条件下快速旋蒸,除去溶剂即得到近无色的细小晶体产物。
本发明的制备方法中,所述三种反应物的摩尔比Cu(CH3CN)4PF6∶Phen∶PPh3为1∶1∶2。
本发明的有益效果首先是所提供的绿色磷光四面体型亚铜配合物Cu(Phen)(PPh3)2(PF6)发光材料,其中芳香性的邻菲罗啉配体刚性很大,非常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,而另一方面大的膦配体三苯基膦导致Cu(I)周围存在较大的空间位阻,从而可以抑制分子激发态的非辐射衰减,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,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,其次是制备绿色磷光Cu(I)配合物Cu(Phen)(PPh3)2(PF6)发光材料的方法,具有工艺简便,所用设备简单,原料简单易得,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.磷光配合物Cu(Phen)(PPh3)2(PF6)分子的单晶结构图。
图2.磷光配合物Cu(Phen)(PPh3)2(PF6)分子在单胞内及其周边空间堆积图。
图3.磷光配合物Cu(Phen)(PPh3)2(PF6)的紫外-可见吸收(UV-Vis)光谱图。
图4.磷光配合物Cu(Phen)(PPh3)2(PF6)的热重-差热(TG-DSC)分析曲线,横坐标表示温度,左侧纵坐标表示重量百分数,右侧纵坐标表示热量。
图5.配合物Cu(Phen)(PPh3)2(PF6)晶体样品在510纳米监控波长下测定的激发谱图。
图6.配合物Cu(Phen)(PPh3)2(PF6)晶体样品在430纳米波长光激发下的光发射谱图。
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Cu(Phen)(PPh3)2(PF6)晶体样品的制备:先称取373mg Cu(CH3CN)4PF6溶解在2mL乙腈和8mL的二氯甲烷混合溶剂中,再称取198mg的Phen和525mg的PPh3配体一起溶解在10mL的二氯甲烷中(所述三种反应物的摩尔比为1∶1∶2),将这两种溶液混合,并搅拌使之充分发生配位反应,最后将所得黄色溶液过滤,并加入正己烷后快速旋蒸除去所有溶剂,真空干燥,得到极浅绿色(近无色)晶体粉末即为产物,产率98%(以Cu计)。
实施例2
合成Cu(I)配合物Cu(Phen)(PPh3)2(PF6)的单晶:先称取37mg Cu(CH3CN)4PF6溶解在2mL乙腈中,再称取20mg的Phen和53mg的PPh3配体一起溶解在3mL的二氯甲烷中,再后者溶液一次加入前者溶液中,搅拌使之完全反应后过滤,将滤液旋蒸后重溶于3ml的二氯甲烷中,在溶液上覆盖正己烷促使产物结晶,静置数天后析出大量极浅绿色条状晶体。挑选一颗0.32mm×0.30mm×0.12mm尺寸的近无色晶体用于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(Phen)(PPh3)2(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,都能发射出强烈的绿光,色坐标值为色坐标值为(0.2505,0.5177),具体的激发光谱和发射光谱如附图5和附图6所示。而对该材料的瞬态荧光测试表明,其发光寿命为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绿色磷光材料,也非常适合用于OLED发光层的绿色磷光材料。
Claims (5)
1.一种绿色磷光四面体型亚铜配合物发光材料,其特征在于:发光材料的结构式为Cu(Phen)(PPh3)2(PF6),式中Phen为电中性含N配体1,10-邻菲罗啉,其分子结构如式(I);式中PPh3为电中性含P配体三苯基膦,其分子结构如式(II):
该发光材料为单斜晶系,P21/n(No.14)空间群,晶胞参数 α=90°,β=92.013(3)°,γ=90°,Z=4,Dc=1.429g/cm3,晶体颜色为浅绿色;配合物表现为离子型配合物,其中的抗衡阴离子为六氟磷酸根,而阳离子则是由亚铜离子和配体Phen、PPh3络合形成的配位阳离子;该配位阳离子中Cu(I)采用CuN2P2四面体配位模式,其中两个N都来自于一个双齿螯合的Phen配体,而两个P来自于两个PPh3配体;其分子结构如式(III):
2.根据权利要求1所述绿色磷光四面体型亚铜配合物发光材料的制备方法,该方法包括以下步骤:
(1)室温下将Cu(CH3CN)4PF6于乙腈和二氯甲烷混合溶剂中完全溶解;
(2)室温下将配体Phen和PPh3的粉末完全溶解于二氯甲烷中;
(3)将所述两种溶液混合,并搅拌使之充分发生配位反应;
(4)将反应液过滤,并加入正己烷后将所得滤液在抽真空条件下快速旋蒸,除去溶剂即得到近无色的细小晶体产物。
3.根据权利要求2所述绿色磷光四面体型亚铜配合物发光材料的制备方法,其特征在于:所述三种反应物的摩尔比Cu(CH3CN)4PF6∶Phen∶PPh3为1∶1∶2。
4.根据权利要求1所述绿色磷光四面体型亚铜配合物发光材料的应用,其特征在于所述发光材料应用于绿光光致发光材料。
5.根据权利要求1所述绿色磷光四面体型亚铜配合物发光材料的应用,其特征在于所述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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CN109776614A (zh) * | 2019-03-25 | 2019-05-21 | 中国计量大学 | 一种对4-甲基吡啶蒸汽选择性响应的亚铜配合物荧光传感材料 |
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CN107011888A (zh) * | 2017-03-21 | 2017-08-04 | 中国计量大学 | 一种晶型的含邻菲罗啉配体四面体型亚铜配合物发光材料 |
CN109776614A (zh) * | 2019-03-25 | 2019-05-21 | 中国计量大学 | 一种对4-甲基吡啶蒸汽选择性响应的亚铜配合物荧光传感材料 |
CN109776614B (zh) * | 2019-03-25 | 2021-03-19 | 中国计量大学 | 一种对4-甲基吡啶蒸汽选择性响应的亚铜配合物荧光传感材料 |
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