CN110337441B - 稀土络合物和发光元件 - Google Patents
稀土络合物和发光元件 Download PDFInfo
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Abstract
本发明公开了一种稀土络合物，其具备稀土离子、和配位于该稀土离子且具有稠合多环芳香族基团的配体。稠合多环芳香族基团是从下述式(I)或(II)所示的稠合多环芳香族化合物中除去氢原子而成的残基，
Description
技术领域
本发明涉及稀土络合物和发光元件。
背景技术
对于显示红光发光的稀土络合物，期待其作为例如构成白色LED光源的荧光体的应用。作为显示红光发光的稀土络合物，已报道了例如具有六氟乙酰丙酮(hfa)衍生物及氧化膦化合物作为配体的铕络合物(专利文献1)。
现有技术文献
专利文献
[专利文献1]日本特开2016-166139号公报
发明内容
发明要解决的问题
强发光性稀土发光体的激发波长能带(吸收波长)通常为400nm以下。另一方面，白色LED光源的发光体的通用性激发波长在由蓝色LED激发的可见光区的460nm附近。如果可以用蓝色LED激发稀土发光体，则从具有优异的高显色性的观点出发，有望创造出一个新的市场。
本发明的主要目的在于提供可基于使用了460nm附近的可见光的激发而有效地发光的新型稀土络合物。
解决问题的方法
本发明的一个方案提供一种稀土络合物，其具备：稀土离子；和配位于该稀土离子、具有稠合多环芳香族基团的配体。所述稠合多环芳香族基团是从下述式(I)或(II)所示的稠合多环芳香族化合物除去键合在式(I)或式(II)中的稠合芳环上的氢原子而成的残基。所述稠合多环芳香族化合物任选具有键合在式(I)或式(II)中的稠合芳环上的取代基。
[化学式1]
本发明还涉及包含上述稀土络合物的发光元件。这样的发光元件作为白光LED、光学相干断层扫描仪的光源等各种光源是有用的。
发明的效果
根据本发明，可提供了可通过使用了可见光(例如，420～480nm)的激发而有效地发光的新型稀土络合物。此外，本发明的一个实施方式的稀土络合物存在在发射光谱中以较窄宽度的发射带显示发光的倾向，这一点对于应用于发光元件也是有利的。
附图说明
图1是Gd(hfa)3(H2O)2和Gd(hfa)3(DPPTO)3的粉体的发射光谱。
图2是Eu(hfa)3(DPPTO)3的粉体的激发和发射光谱。
图3是示出了Eu(hfa)3(DPPTO)3和Eu(hfa)3(HPO)2的吸收强度×发光效率与波长之间的关系的计算结果的图。
图4是示出了Eu(hfa)3(DPPTO)3和所设计的稀土络合物的吸收强度与波长之间的关系的计算结果的图。
图5是Eu2(hfa)6(BDPPC)2的粉体的激发和发射光谱。
图6是以低浓度包含Eu2(hfa)6(BDPPC)2的氯仿溶液的吸收光谱。
具体实施方式
在下文中，详细描述本发明的实施方式。但本发明不限于以下实施方式。
一个实施方式的稀土络合物具备稀土离子、和与该稀土离子配位的多个配体。
稀土离子例如是选自铕(Eu)、钕(Nd)、镱(Yb)及钆(Gd)中的稀土元素的离子。例如，铕作为三价阳离子(Eu3+)而形成络合物。
一个实施方式的稀土络合物具有配体，该配体具有由下述式(I)或(II)所示的稠合多环芳香族化合物衍生的稠合多环芳香族基团。稠合多环芳香族基团是从式(I)或(II)所示的稠合多环芳香族化合物除去键合在式(I)或式(II)中的稠合芳环上的氢原子而成的残基。式(I)或(II)的稠合多环芳香族化合物和由其衍生的稠合多环芳香族基团可以具有或者不具有键合在式(I)或式(II)中的稠合芳环上的取代基(例如甲基)。这样的稠合多环芳香族基团具有较大的面积和较大宽度的π共轭体系，这有助于通过使用了460nm附近的可见光的激发进行有效的发光。该事实可根据基于半经验分子轨道法的吸收特性的计算而得到证实。
[化学式2]
作为从式(I)的稠合多环芳香族化合物除去氢原子而成的残基即缩合多环芳香族基团的具体例，可举出：下述式(Ia)所示的一价稠合多环芳香族基团和下述式(Ib)所示的二价稠合多环芳香族基团。这些式中的*表示键合臂，这也适用于其他式。
[化学式3]
作为从式(II)的稠合多环芳香族化合物除去氢原子而成的残基的缩合多环芳香族基团的具体例可举出：下述式(IIa)所示的一价稠合多环芳香族基团、及下述式(IIb)所示的二价稠合多环芳香族基团。
[化学式4]
具有稠合多环芳香族基团的配体例如可以是下述式(10)所示的氧化膦配体、或下述式(20)所示的二酮配体中的至少任一种。
[化学式5]
在式(10)中，Z表示由上述式(I)或(II)的稠合多环芳香族化合物衍生的稠合多环芳香族基团，R11和R12各自独立地表示与所述稠合多环芳香族基团不同的芳基。在式(20)中，Z表示由上述式(I)或(II)的稠合多环芳香族化合物衍生的稠合多环芳香族基团，R21和R22各自独立地表示氢原子、烷基、卤代烷基、与所述稠合多环芳香族基团不同的芳基、或杂芳基。
作为R11或R12的芳基可以是从芳香族化合物除去一个氢原子而成的残基。芳基的碳原子数例如为6～14。作为芳基的具体例，可举出：从取代或未取代的苯、取代或未取代的萘、取代或未取代的蒽、或取代或未取代的菲除去一个氢原子而成的残基。特别是，R11和R12可以是取代或未取代的苯基。
作为R21或R22的烷基及卤代烷基的碳原子数可以为1～15、1～5、或1～3。卤代烷基可以是三氟甲基等氟代烷基。作为R21或R22的芳基及杂芳基例如可举出：苯基、萘基、及噻吩基。R21可以是甲基、三氟甲基、叔丁基或苯基。R22可以是氢原子(也包括氘原子)。
具有稠合多环芳香族基团的配体例如可以是下述式(30)所示的双齿的氧化膦配体。式(30)中的Z、R11及R12与式(10)中的Z、R11及R12同样地定义。式(30)的氧化膦配体可以与两个稀土离子配位而将这些稀土离子连接。
[化学式6]
除具有稠合多环芳香族基团的配体之外，稀土络合物还可以进一步具有其他配体。作为其他配体的例子，可举出下述式(11)所示的氧化膦配体及下述式(21)所示的二酮配体。
[化学式7]
[化学式8]
式(11)中，R13、R14及R15各自独立地表示与由所述式(I)或(II)的稠合多环芳香族化合物衍生的稠合多环芳香族基团不同的芳基。作为R13、R14或R15的芳基的例子可举出与式(10)中的R11和R12相同的那些。R13、R14及R15可以是取代或未取代的苯基。
式(21)中，R23、R24及R25各自独立地表示氢原子、烷基、卤代烷基、与由所述式(I)或(II)的稠合多环芳香族化合物衍生的稠合多环芳香族基团不同的芳基、或杂芳基。作为R23、R24及R25的例子，可举出与式(20)中的R21、R22同样的那些。R23和R25可以各自独立地为甲基、三氟甲基、叔丁基或苯基，R24可以为氢原子(也包括氘原子)。
包含式(20)或式(21)所示的二酮配体的稀土络合物从强发光等观点出发可具有更优异的特性。因此，作为稀土络合物的配体，可以选择式(20)所示的具有稠合多环芳香族基团的二酮配体和式(11)所示的氧化膦配体的组合、或式(21)所示的二酮配体和式(10)所示的具有稠合多环芳香族基团的配体的组合。例如，稀土络合物可以是下述式(C1)或(C2)所示的络合物。在式(C1)和(C2)中，Ln(III)表示三价稀土离子。
[化学式9]
具有二酮配体的稀土络合物可以具有式(30)所示的双齿配体。该例子是下述(C3)所示的络合物。式(C3)中的各符号的定义与上述同义。在式(C3)所示的络合物中，两个稀土离子Ln(III)通过两个双齿配体连接在一起。
[化学式10]
包含本实施方式的稀土络合物的发光元件可期待应用于例如蓝色LED激发型的白色LED元件、光学相干断层扫描仪(OCT)的光源。一些实施方式的稀土络合物可以以低成本提供具有140nm以上或200nm以上的宽带域宽度的发光元件。带域宽度直接影响例如OCT的分辨率，可通过宽带域宽度的光源而得到高分辨率。
实施例
在下文中，参考实施例更具体地描述本发明。但本发明不限于这些实施例。
1.稀土络合物的合成
(1)Gd(hfa)3(DPPTO)3的合成
将三(六氟乙酰丙酮)钆(Gd(hfa)3(H2O)2，350mg，0.430mmol)和2-二苯基磷酰基苯并菲DPPTO(500mg，1.17mmol)溶解在甲苯(15mL)中，将得到的反应溶液在85℃下加热回流12小时。随后，用蒸发器使反应溶液干固。使用二氯甲烷/己烷的混合溶剂对残渣进行再沉淀，用己烷洗涤沉淀物，得到了Gd(hfa)3(DPPTO)3(白色粉体)(产量78mg，产率13％)。
元素分析(％):calcd for C105H66GdF18O9P3:C 61.11,H 3.22.Found:C 62.53,H3.53.
ESI-MS:m/z calcd for C100H65GdF12O7P3[M-hfa]+＝1856.30；found:1856.35.
(2)Eu(hfa)3(DPPTO)3的合成
将三(六氟乙酰丙酮)铕(Eu(hfa)3(H2O)2，350mg，0.430mmol)和2-二苯基磷酰基苯并菲(DPPTO，300mg，0.701mmol)溶解在甲苯(10mL)中，将得到的反应溶液在85℃下加热回流12小时。随后，用蒸发器使反应溶液干固。使用二氯甲烷/己烷的混合溶剂对残渣进行再沉淀，用己烷洗涤沉淀物，得到了Eu(hfa)3(DPPTO)3(白色粉体)(产量82mg，产率17％)。
元素分析(％)：calcd for C105H66EuF18O9P3:C 61.26,H 3.23.Found:C 61.40,H3.41
ESI-MS:m/z calcd for C100H65EuF12O7P3[M-hfa]+＝1851.30；found:1851.32.
[化学式11]
(3)Eu2(hfa)6(BDPPC)2的合成
1,6-双(二苯基磷酰基)晕苯(BDPPC)的合成
使晕苯(6.3g，20.9mmol)悬浮在氯苯(300mL)中，向其中滴加氯苯(100mL)和溴(10.0g，62.6mmol)的混合物。将形成的反应液在搅拌下于70℃加热15分钟，然后冰冷20分钟。结束搅拌并静置反应液，进行了倾析。将通过抽滤取出的固体用氯苯和己烷洗涤，然后干燥，得到了含有二溴晕苯的黄色固体(7.4g)。
使得到的黄色固体悬浮在超脱水THF(250mL)中。向其中加入正丁基锂(8.5mL，14mmol)，搅拌悬浮液。2小时后，加入氯二苯基膦(2.4mL，13mmol)时，悬浮液变为透明溶液。向该溶液中加入H2O2(2mL)，进行了3小时搅拌。然后用二氯甲烷和盐水从溶液中萃取了三次。将二氯甲烷层干固，对得到的粗产物的固体利用硅胶柱色谱(二氯甲烷/乙酸乙酯)进行纯化，得到了BDPPC。
1H-NMR(CDCl3,400MHz):/ppm＝10.03-8.60(m,10H),7.99-7.40(m,20H)
Eu2(hfa)6(BDPPC)2的合成
将三(六氟乙酰丙酮)铕(Eu(hfa)3(H2O)2，65mg，0.08mmol)和BDPPC(50mg，0.07mmol)溶解在二氯甲烷(20mL)中，将得到的反应溶液在室温下搅拌4小时。随后，用蒸发器使反应溶液干固。通过使用了二氯甲烷/己烷的混合溶剂的重结晶对凝固得到的粗产物进行纯化，得到了Eu2(hfa)6(BDPPC)2(黄色粉体)(产量10mg，产率5％)。
ESI-MS:m/z calcd for C121H65Eu2F30O14P4[M-hfa]+＝2740.13；found:2740.08.
[化学式12]
2.Gd(hfa)3(DPPTO)3的光物理性质
图1是Gd(hfa)3(H2O)2和Gd(hfa)3(DPPTO)3的粉体的发射光谱。激发波长λex为280nm或380nm。在Gd(hfa)3(H2O)2的发射光谱中，在470nm附近观察到了源自hfa的磷光。在Gd(hfa)3(DPPTO)3的发射光谱中，当激发光为280nm时，在370nm附近和470nm附近观察到了发射带。由于短波长侧的发射带与配体的DPPTO单质的荧光一致，因此认为其源自络合物中DPPTO配体的荧光。由于长波长侧的发射带与Gd(hfa)3(H2O)2中hfa的磷光带的波长区重叠，因此可认为主要观察到了hfa配体的磷光。另一方面，当激发光为380nm时，在430nm附近观察到Gd(hfa)3(DPPTO)3的发射带。由于该发射带的能量接近于DPPTO配体单体(溶液或粉体条件)的T1状态的能量，因此可认为430nm附近的发射带主要是由Gd(hfa)3(DPPTO)3中的DPPTO配体的磷光带来的。这些结果表明，当用波长为380nm的光激发Gd(hfa)3(DPPTO)3时，主要会形成DPPTO配体的激发三重态。
3.Eu(hfa)3(DPPTO)3的光物理性质
<激发发射光谱>
图2是Eu(hfa)3(DPPTO)3的粉体的激发和发射光谱。图2的上侧的光谱表示荧光波长λem为610nm的激发光谱、及激发波长λex为380nm的发射光谱。图2的下侧的光谱表示激发波长λex为280nm的发射光谱。当激发波长为380nm时，在579nm、593nm、613nm、650nm、700nm处可观察到发射带，它们分别对应于5D0→7F0、5D0→7F1、5D0→7F2、5D0→7F3、5D0→7F4。
在激发波长为380nm的发射光谱中，在445nm附近观察到了较宽的发射带。该波长发生了向比根据Gd(hfa)3(DPPTO)3的发射光谱估算的DPPTO的磷光波长(439nm)更长的波长侧的位移。这表明，基于从DPPTO配体向Eu(III)的跃迁的LMCT激发态与T1态发生了混合。
在激发波长为280nm的发射光谱中，与Gd(hfa)3(DPPTO)3同样地，在370nm附近观察到了DPPTO的荧光。这表明，DPPTO配体实际上不受到Eu(III)的内部重原子效应。
<发光寿命>
测定了Eu(hfa)3(DPPTO)3的粉体条件下的发光寿命。表1示出了观察到的发光寿命τobs、根据发光寿命测定求得的4f-4f跃迁的发光量子产率Φff、π-π*跃迁的发光量子效率Φππ*、辐射常数kr、非辐射常数knr、以及能量转移效率ηsens。表1中还一并示出了关于Eu(hfa)3(TPPO)2的文献值(A.Nakajima,T.Nakanishi,Y.Kitagawa,T.Seki,H.Ito,K.Fushimi,Y.Hasegawa,Sci.Rep.6,24458(2016))。
[表1]
[化学式13]
与Eu(hfa)3(TPPO)2相比，Eu(hfa)3(DPPTO)3显示出了更高的发光量子产率Φff。
4.基于模拟的吸收强度的评价
通过模拟，将Eu(hfa)3(DPPTO)3的光吸收特性与Eu(hfa)3(HPO)2进行了比较。使用量子化学计算软件Gaussian、通过半经验分子轨道法进行了模拟。图3是示出了Eu(hfa)3(DPPTO)3及Eu(hfa)3(HPO)2的吸收强度×发光效率与波长之间的关系的计算结果的图。图中，A是Eu(hfa)3(DPPTO)3，X是Eu(hfa)3(HPO)2。该图表明，与Eu(hfa)3(HPO)2相比，Eu(hfa)3(DPPTO)3在460nm附近表现出约15倍的发光强度。
[化学式14]
进一步，设计具有包含稠合多环芳香族基团的二酮配体的下述稀土络合物(络合物B和络合物C)，通过模拟计算出它们的光吸收特性。图4是示出了Eu(hfa)3(DPPTO)3、络合物B及络合物C的吸收强度与波长之间的关系的计算结果的图。图中，A是Eu(hfa)3(DPPTO)3，B是络合物B，C是络合物C。该图表明，即使与Eu(hfa)3(DPPTO)3相比，络合物B和络合物C在460nm附近也显示出大幅增加的发光强度。
[化学式15]
[化学式16]
5.Eu2(hfa)6(BDPPC)2的光物理性质
图5是Eu2(hfa)6(BDPPC)2的粉体的激发和发射光谱。图5示出了荧光波长λem为613nm的激发光谱、及激发波长λex为450nm的发射光谱。确认了：Eu2(hfa)6(BDPPC)2的粉体在460nm的激发光下表现出最强的发光强度，在500nm左右的长波长的激发光下也发光。
测定Eu2(hfa)6(BDPPC)2在氯仿中的摩尔吸光系数ε、以及在对有机配体进行激发时Eu(III)的发光效率(室温)。图6是以低浓度包含Eu2(hfa)6(BDPPC)2的氯仿溶液的吸收光谱。制备Eu(hfa)3(TPPO)2的氘代氯仿溶液和Eu(hfa)3(HPO)2的氯仿溶液，测定了它们的摩尔吸光系数和发光效率。
[表2]
a:Eu(hfa)3(HPO)2的发光效率以粉体进行测定
表2所示的结果表明，Eu2(hfa)6(BDPPC)2通过450nm的激发光，以相比于Eu(hfa)3(TPPO)2为约2000倍、相比于Eu(hfa)3(HPO)2为约200倍的强度发光。在460nm的激发光的情况下也同样地，可认为Eu2(hfa)6(BDPPC)2表现出强发光强度。当用458nm的蓝色光照射Eu2(hfa)6(BDPPC)2的氯仿溶液时，观察到了Eu(III)的强红色发光。
工业实用性
本发明的稀土络合物及包含该稀土络合物的发光元件作为蓝色LED型的白色LED、OCT用光源是有用的。此外，还可期待应用于：利用了发光特性由于溶剂种类的变化的溶剂传感器、利用了温度变化特性的温度传感器、以及圆偏振光发光体。
Claims (3)
1.一种稀土络合物，其具备：
稀土离子、和
配位于该稀土离子、具有稠合多环芳香族基团的配体，
其中，所述稠合多环芳香族基团是从下述式(II)所示的稠合多环芳香族化合物除去键合在式(II)中的稠合芳环上的氢原子而成的残基，所述稠合多环芳香族化合物任选具有键合在式(II)中的稠合芳环上的取代基，所述取代基为甲基，
所述具有稠合多环芳香族基团的配体是下述式(30)所示的双齿的氧化膦配体，该氧化膦配体与两个所述稀土离子配位，
式(30)中，Z表示所述稠合多环芳香族基团，R11和R12各自独立地表示与所述稠合多环芳香族基团不同的芳基。
2.根据权利要求1所述的稀土络合物，其中，
该稀土络合物还具备下述式(21)所示的二酮配体，该二酮配体配位于所述稀土离子，
式(21)中，R23、R24及R25各自独立地表示氢原子、烷基、卤代烷基、与所述稠合多环芳香族基团不同的芳基、或杂芳基。
3.一种发光元件，其包含权利要求1或2所述的稀土络合物。
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018155557A1 (ja) | 2018-08-30 |
| US11499093B2 (en) | 2022-11-15 |
| US20200063030A1 (en) | 2020-02-27 |
| EP3587429A1 (en) | 2020-01-01 |
| JPWO2018155557A1 (ja) | 2020-01-09 |
| JP7063484B2 (ja) | 2022-05-09 |
| EP3587429A4 (en) | 2020-11-25 |
| CN110337441A (zh) | 2019-10-15 |
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