氟代吡啶甲酸解离的环金属铱配合物及其电致化学发光性能

潘淼; 胡媛媛; 张曼; 童碧海; 张千峰; 周会东; 时鹏

doi:10.3788/fgxb20194006.0735

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氟代吡啶甲酸解离的环金属铱配合物及其电致化学发光性能

材料合成及性能 | 更新时间：2020-08-12

- 氟代吡啶甲酸解离的环金属铱配合物及其电致化学发光性能
- Electrochemiluminescence Properties of Cylcometalated Iridium(Ⅲ) Complexes Containing Fluorinated Picolinic Acid Ancillary Ligands
- 发光学报 2019年40卷第6期页码：735-742
- 作者机构：
  
  安徽工业大学冶金工程学院, 分子工程与应用化学研究中心, 冶金减排与资源综合利用教育部重点实验室, 安徽马鞍山 243002
- 作者简介：
- 基金信息：
  
  国家自然科学基金（21572001）();安徽省大学生创新创业训练项目（201710360153）资助()
- DOI：10.3788/fgxb20194006.0735
  中图分类号： O641.4
- 纸质出版日期：2019-6-5，
  
  网络出版日期：2018-10-11，
  
  收稿日期：2018-6-27，
  
  修回日期：2018-9-21，
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潘淼, 胡媛媛, 张曼等. 氟代吡啶甲酸解离的环金属铱配合物及其电致化学发光性能[J]. 发光学报, 2019,40(6): 735-742

PAN Miao, HU Yuan-yuan, ZHANG Man etc. Electrochemiluminescence Properties of Cylcometalated Iridium(Ⅲ) Complexes Containing Fluorinated Picolinic Acid Ancillary Ligands[J]. Chinese Journal of Luminescence, 2019,40(6): 735-742
潘淼, 胡媛媛, 张曼等. 氟代吡啶甲酸解离的环金属铱配合物及其电致化学发光性能[J]. 发光学报, 2019,40(6): 735-742 DOI： 10.3788/fgxb20194006.0735.

PAN Miao, HU Yuan-yuan, ZHANG Man etc. Electrochemiluminescence Properties of Cylcometalated Iridium(Ⅲ) Complexes Containing Fluorinated Picolinic Acid Ancillary Ligands[J]. Chinese Journal of Luminescence, 2019,40(6): 735-742 DOI： 10.3788/fgxb20194006.0735.

摘要

以2-苯基吡啶为主配体、以氟修饰的吡啶-2-甲酸为辅助配体合成出一系列环金属中性铱配合物。产物结构通过核磁及质谱进行了确认，对其光物理性能研究表明，这些配合物的发光波长在498~516 nm之间，属于绿光发射。没有氟取代的配合物

Ir1

量子效率最高，达到32%，而由于2位氟取代的位阻影响

Ir4

的量子效率最低只有6%，其他氟取代配合物的量子效率在13%~16%之间。引入氟原子后配合物的氧化电位都有所增加，氧化电位由511 mV增加到547~574 mV之间。热稳定性也在氟取代后增加，由142℃提高到187~380℃之间，

Ir4

提高的最少，为187℃。应用于电致化学发光时，除

Ir4

外，氟取代都能增加其电致化学发光强度，由332增加到333~370之间。而配合物

Ir4

的发光强度只有203。以上结果表明氟取代的效果跟位置有很大关系，2位氟取代由于位阻效应，使配合物的量子效率及稳定性都有不利影响，而其他位置的取代则能提高配合物的这些性能。该研究结果对设计开发综合性能优异的发光材料具有借鉴意义。

Abstract

A series of neutral cyclometalated iridium(Ⅲ) complexes(

Ir1

Ir5

)

which containing 2-phenylpyridine main ligand and fluorinated picolinic acid ancillary ligands

were synthesized with main ligand of 2-phenylpyridine and ancillary ligand of 2-pyridine carboxylic acid. The structures of the complexes were confirmed by the NMR and mass spectroscopies. All these complexes displayed intense green phosphorescent emission with the emission maximum between 498 nm and 516 nm. The quantum efficiency of reference complex

Ir1

is 32.0%. Due to the influence of the 2-position fluorine substituent

complex

Ir4

has the lowest quantum efficiency of 6.0%. The quantum efficiency of other fluorinated complexes are between 13.0% and 16.0%. Compared with the reference complex

Ir1

the oxidation potential of fluorinated complexes increased from 511 mV to 547-574 mV and the thermal stability enhanced from 142℃ to 187-380℃. The thermal stability increase of

Ir4

is the minimum(187℃). The ECL intensity of reference complex

Ir1

was 332. Except

Ir4

the ECL intensity of complexes

Ir2

Ir5

is higher than reference complex

Ir1

which is between 333 and 370. Complex

Ir4

has the lowest ECL intensity of 203. All these results show the influence of fluorine substituent is related to the substituent positions in picolinic acid. The 2-position fluoro-substitution can reduce the quantum efficiency and thermal stability because of the steric effect. Relatively

fluoro-substitution on other positions can enhance these two performances. This research can be used as a reference in the design and development of efficient luminescent materials.

关键词

环金属铱配合物吡啶甲酸氟化学电致化学发光

Keywords

cyclometalated iridium(Ⅲ) complexpyridine carboxylic acidfluorineelectrochemiluminescence

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