CN108676555B - 一种含铕离子液体红光材料及制备方法和应用 - Google Patents

一种含铕离子液体红光材料及制备方法和应用 Download PDF

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CN108676555B
CN108676555B CN201810518522.9A CN201810518522A CN108676555B CN 108676555 B CN108676555 B CN 108676555B CN 201810518522 A CN201810518522 A CN 201810518522A CN 108676555 B CN108676555 B CN 108676555B
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唐斯甫
侯晓敏
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Qingdao Agricultural University
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Abstract

一种含铕离子液体红光材料的制备及其在光致发光材料方面的应用。该离子液体化合物的化学式为[bmim][Eu(HFDK)4]，其中bmim为1‑丁基‑4‑甲基咪唑，HFDK为6,6,7,7,8，8,8‑七氟‑2,2‑二甲基辛烷‑3,5‑二酮。其分子量为1471.90，属单斜晶系，空间群为P2(1)c，单胞参数为a=10.714(2)Å，b=21.902(4)Å，c=26.285(5)Å，alpha=90o，beta=100.80(3)o，gamma=90o，V＝6059(2)Å3，Z＝4。采用一锅法制备，以水‑乙醇混合溶剂为溶剂。室温下为无色块状晶体，熔点为98.0 oC，凝固点为73.5 oC。在紫外及近紫外光激发下，显示出很强的红色光，荧光寿命为0.73 ms(λex=334,λem=612 nm)。本发明还公开了制备方法。

Description

一种含铕离子液体红光材料及制备方法和应用
技术领域
本发明属于离子液体的制备与应用研究，具体涉及一种β-二酮类含铕离子液体化合物。
本发明还涉及一种制备上述含铕离子液体的方法。
本发明还涉及上述含铕离子液体的应用。
背景技术
离子液体是一类由阴阳离子组成，且熔点低于100 oC的熔盐。具有蒸汽压小、电化学窗口宽、无（低）毒、不可燃等特点，被认为是一种绿色溶剂；由于离子液体由阴阳离子组成，通过阴阳离子的选择性组合，可调节其物理化学性质，因此也被称为可“设计”溶剂。离子液体在有机合成、电化学、光学等领域有着广泛的实际和潜在应用前景。
当前离子液体主要是作为一种替代传统有机分子溶剂的新型绿色溶剂，但这远远没有充分发挥离子液体的优点。多数离子液体化合物是无色透明的，比较适合用于光学领域。此外，由于一些阴离子具有配位能力，通过向离子液体中引入一种稀土离子，与原有的阴离子形成配位阴离子，可以得到一种含有稀土离子的新型离子液体化合物。稀土离子的引入使得离子液体不仅具有传统离子液体化合物的诸多优点，而且被赋予了稀土离子的性能，比如发光、磁性、催化性能等。
稀土发光材料具有谱线窄、色度纯等优点，但三价稀土离子的4f-4f跃迁是禁阻的，吸光系数小，吸收和发射光谱强度弱，通过引入具有共轭结构的配体可以克服这一弱点。β-二酮配体具有较强的与稀土离子配位能力，吸光系数大，能量传递效率高，是较为理想的制备高性能光致发光材料的配体。6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮是一种不对称的氟代β-二酮配体。采用不对称的β-二酮配体可以有效降低所得离子液体化合物的熔点，同时氟代可以有效减少高频振动（N-H, O-H, C-H等）所造成的能量损失。因此，本发明希望通过以6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮为配体，与铕离子和1-丁基-4-甲基咪唑阳离子构筑新型含铕离子液体化合物，用于光致发光研究。有关这方面的研究尚未见文献报道。
发明内容
本发明的目的在于制备一种具有优异光致发光性能的的含铕离子液体化合物材料。
为实现上述目的，本发明所提供的含铕离子液体化合物，其化学表达式为[bmim][Eu(HFDK)4]，其中bmim为1-丁基-4-甲基咪唑，HFDK为6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮。
所述的含铕离子液体，其单晶晶胞参数为：单斜晶系，空间群为P2(1)c， a=10.714(2)Å，b=21.902(4)Å，c= 26.285(5)Å，alpha = 90o，beta = 100.80(3)o，gamma = 90o，V＝6059(2)Å3，Z＝4。
该离子液体化合物由阴阳离子组成，阳离子为1-丁基-4-甲基咪唑阳离子，阴离子为[Eu(HFDK)4]-配位阴离子。阴离子中Eu(III)离子处于中心，与四个HFDK配体的8个氧原子形成反四棱柱配位构型。
本发明提供的制备上述离子液体的方法，采用一锅法制备，以6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮、六水合氯化铕和氯化1-丁基-4-甲基咪唑为原料，以水-乙醇混合溶剂为溶剂，在50-60 oC搅拌30min，冷至室温，即析出无色块状晶体，过滤。
本发明提供的含铕离子液体，可以作为一种红光发光材料。
该含铕离子液体材料对水和空气不敏感，热重和粉末衍射测试表明，该含铕离子液体具有较好的热稳定性。熔点为98.0 oC，凝固点为73.5 oC。
光致发光性能测试表明，该含铕离子液体在334nm光激发下显示很强的红色，预示着该材料可以作为一种光致发光“软材料”，在发光材料领域具有很好的应用前景。
附图说明
图1 本发明的含铕离子液体[C4mim][Eu(HFDK)4]的室温和77K固态发射光谱图。
图2 本发明的含铕离子液体[C4mim][Eu(HFDK)4]的CIE坐标图。
具体实施方式
本发明所得到的含铕离子液体化合物（C48H55EuF28N2O8），分子量为1471.90，属单斜晶系，空间群为P2(1)c，单晶晶胞参数为a=10.714(2)Å，b=21.902(4)Å，c= 26.285(5)Å，alpha = 90o，beta = 100.80(3)o，gamma = 90o，V＝6059(2)Å3，Z＝4。
该含铕离子液体化合物中中心铕离子为8配位，与4个HFDK配体螯合配位，形成反四棱柱配位构型。
该含铕离子液体在乙醇-水混合溶剂中制备：将bmimCl (0.1747 g, 1 mmol)，6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮（HHFDK, 1.1847 g, 4 mmol），4mL 1M NaOH（4mmol）水溶液加入6mL乙醇中，搅拌并升高温度至50 oC，直至全部溶解。称取六水合氯化铕（0.3664 g, 1 mmol）溶于2mL水中，逐滴加入上述溶液中，继续搅拌30 min，得澄清溶液，停止搅拌，冷却至室温，得到无色块状晶体。
该含铕离子液体材料对水和空气不敏感，热重和粉末衍射测试表明，该含铕离子液体具有较好的热稳定性。
实例1
bmimCl (0.1747 g, 1 mmol)，6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮（HHFDK, 1.1847 g, 4 mmol），4mL 1M NaOH（4mmol）水溶液加入6mL乙醇中，搅拌并升高温度至50 oC，直至全部溶解。称取六水合氯化铕（0.3664 g, 1 mmol）溶于2mL水中，逐滴加入上述溶液中，继续搅拌30 min，得澄清溶液，停止搅拌，冷却至室温，得到无色块状晶体。
实例2
bmimCl (0.1747 g, 1 mmol)，6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮（HHFDK, 1.1847 g, 4 mmol），4mL 1M NaOH（4mmol）水溶液加入6mL乙醇中，搅拌并升高温度至60 oC，直至全部溶解。称取六水合氯化铕（0.3664 g, 1 mmol）加入上述溶液中，继续搅拌30 min，得澄清溶液，停止搅拌，冷却至室温，得到无色块状晶体。
实例3
bmimCl (0.1747 g, 1 mmol)，6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮（HHFDK, 1.1847 g, 4 mmol），NaOH（0.1600 g, 4mmol）水溶液加入10mL乙醇-水混合溶剂中（v/v=3:2），搅拌并升高温度至60 oC，直至得到澄清溶液。称取六水合氯化铕（0.3664 g,1 mmol加入上述溶液中，继续搅拌30 min，得澄清溶液，停止搅拌，冷却至室温，得到无色块状晶体。
实例4
光致发光性能：
在298 K，以334nm激发光激发，该离子液体化合物显示出Eu(III)的特征红色，发射波长为：587.75, 593.50, 612.00, 615.75, 650.25, 656.00, 701.00 nm，其CIE坐标为：0.577, 0.328。其室温固态发射光谱图和CIE坐标图分别见图1 和图2。
实例5
光致发光性能：
在77 K，以334nm激发光激发，该含铕离子液体化合物显示出典型的红色，发射波长为：579.50, 585.50, 588.75, 593.50, 595.25, 612.25, 616.50, 619.50, 623.25,634.50, 651.00, 656.25, 673.25, 690.00, 692.50, 696.00, 701.00 nm，其CIE坐标为：0.610, 0.335。其低温固态发射光谱图和CIE坐标图分别见图1 和图2。

Claims (6)

1.一种含铕离子液体红光材料，其特征在于它的化学式为：[bmim][Eu(HFDK)4]，其中bmim为1-丁基-4-甲基咪唑，HFDK为6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮；
单斜晶系，空间群为P2(1)c，单晶晶胞参数为a=10.714(2)Å，b=21.902(4)Å，c= 26.285(5)Å，alpha = 90o，beta = 100.80(3)o，gamma = 90o，V＝6059(2)Å3，Z＝4；
所述材料的制备方法为：采用一锅法制备，以6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮、六水合氯化铕和氯化1-丁基-4-甲基咪唑为原料，以水-乙醇混合溶剂为溶剂，在50-60℃搅拌30min，冷至室温即析出无色块状晶体，过滤。
2.如权利要求1所述的含铕离子液体红光材料，其特征在于：6,6,7,7,8,8,8-七氟-2,2-二甲基辛烷-3,5-二酮、六水合氯化铕和氯化1-丁基-4-甲基咪唑的摩尔比为：4:1:1。
3.如权利要求1所述的含铕离子液体红光材料，其特征在于：所述材料在室温下为无色块状晶体，熔点为98.0℃，凝固点为73.5℃。
4.如权利要求1所述的含铕离子液体红光材料，其特征在于：在紫外及近紫外光激发下，所述材料显示Eu(III)特征红色。
5.如权利要求1所述的含铕离子液体红光材料，其特征在于：所述材料在298K时发射波长为：587.75，593.50，612.00，615.75，650.25，656.00，701.00nm，CIE坐标为：0.577，0.328；77K时发射波长为：579.50，585.50，588.75 ，593.50，595.25，612 .25，616.50，619.50，623.25，634.50，651.00，656.25 , 673.25，690.00，692.50，696.00，701.00 nm，CIE坐标为：0.610，0.335。
6.权利要求1所述的含铕离子液体红光材料的用途，其特征在于：该材料可以用作红色发光材料。
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