Citation: Ma Mingshuo, Zou Luyi, Li Yan, Ren Aimin, Ding Xiaoli. Theoretical Studies on Photophysical Properties of Isomeric Iridium(Ⅲ) Complexes Ir(ppy)₂(acac) Containing Dimesitylboron Moiety[J]. Acta Chimica Sinica, ;2016, 74(9): 764-772. doi: 10.6023/A16060308 shu

Theoretical Studies on Photophysical Properties of Isomeric Iridium(Ⅲ) Complexes Ir(ppy)₂(acac) Containing Dimesitylboron Moiety

Ma Mingshuo ^a,b ,
Zou Luyi ^a ,
Li Yan ^c ,
Ren Aimin ^a,*,, ,
Ding Xiaoli ^a

a.
Institute of Theoretical Chemistry, Jilin University, Changchun 132023
b.
Center of Analysis and Measurement, Jilin Institute of Chemical Technology, Jilin City 132022
c.
School of Chemical and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin City 132022

Corresponding author: Ren Aimin, aimin_ren@yahoo.com
Received Date: 24 June 2016

Fund Project: Youth Program of National Natural Science Foundation of China 11504130National Basic Research Program of China (973 Program) 2013CB834801National Natural Science Foundation of China 20973078National Natural Science Foundation of China 21473071National Natural Science Foundation of China 21173099

Figures(4)

The phosphorescent photophysical properties for three Ir(Ⅲ) complexes 1～3 containing dimesitylboryl moiety were investigated by DFT. The electronic structure of the ground and excited state, absorption and emission spectra, the spin-orbital coupling matrix < T₁^α|H_SOC|S_n >, the radiative and non-radiative transition process for complexes 1～3 were calculated by DFT/TD-DFT approach. The effect of dimesitylboryl substitution at different site of Ir(Ⅲ) complex with phenylpyridine and acetylacetone ligand on the phosphorescent radiative and non-radiative process was discussed. The results reveal that the introduction of B(Mes)₂ group to the pyridine ring of the phenylpyridine (ppy) ligand can strengthen the interactions between the metal and the acetylacetone (acac) ligand, reduce the structure relaxation of the molecule from the ground state to the excited triplet state, and maintain the structures of octahedral field, which is conducive to restricted non-radiative transition. Moreover the singlet-triplet energy splitting ΔE(S₁-T₁) is decreased, the intersystem crossing rate and radiative transition rate are increased. In addition, compared with the substitution at the pyridinyl in complex 1, modifying phenyl group with B(Mes)₂ group in complex 2 and 3 could induce larger structural changes from S₀ to T₁ state and enhance the < S₀|H_SOC|T₁ > value, the spin orbit coupling matrix element between S₀ and T₁ state of 2 and 3 are greater than that of 1, which will induce a larger non-radiative transition rate for 2 and 3. The variety of substitution position of B(Mes)₂ group leads to different d-splitting, different spin-orbital coupling effect in the x, y or z direction, induces the changes of zero field splitting energy and the inequality of radiative transition rates in the three substates (namely, k_r^x, k_r^y, and k_r^z), and the largest radiative rates of 1～3 are all located in z substates with values of 2.32×10⁵, 1.20×10⁵, and 5.50×10⁵ s^-1, respectively. Therefore, we explained the reason that complex 1 has higher phosphorescence quantum efficiency through modifying the pyridine ring of the ppy ligand rather than the benzene ring.
- B(Mes)₂,
- spin-orbit coupling,
- radiative transition rate,
- phosphorescence quantum efficiency
1. [1]
  Yersin, H.; Finkenzeller, W. J.; Walter, M. J.; Lupton, J. M.; Djurovich, P. I.; Thompson, M. E.; Tsuboyama, A.; Okada, S.; Ueno, K.; Chi, Y.; Chou, P. T.; Yang, X. H.; Jaiser, F.; Neher, D.; Xiang, H. F.; Lai, S. W.; Lai, P. T.; Che, C. M.; Tanaka, I.; Tokito, S.; Dijken, A. V.; Brunner, K.; Börner, H.; Langeveld B. M. W.; Mak, C. S. K.; Chan, W. K.; Nazeeruddin, M. K.; Klein, C.; Grätzel, M.; Zuppiroli, L.; Berner, D.; Bian, Z. Q.; Huang, C. H. Highly Efficie nt OLEDs with Phosphorescent Materials, Wiley-VCH, 1st edn, Weinheim, 2008.
2. [2]
  Templier, F. OLED Microdisplays: Technology and Applications, Chapter: OLED Theory and Principles, Wiley-VCH, 1st edn, Weinheim, 2014.
3. [3]
  Förrest, S. R.; Baldo, M. A.; O'Brien, D. F.; You, Y.; Shoustikov, A.; Sibley, S.; Thompson, M. E. Nature 1998, 395, 151. doi: 10.1038/25954
4. [4]
  Hudson, Z. M.; Sun, C.; Helander, M. G.; Amarne, H.; Lu, Z. H.; Wang, S. Adv. Funct. Mater. 2010, 20, 3426. doi: 10.1002/adfm.v20:20
5. [5]
  Zhou, G. J.; Ho, C. L.; Wong, W. Y.; Wang, Q.; Ma, D. G.; Wang, L. X.; Lin, Z. Y.; Marder. T. B.; Beeby, A. Adv. Funct. Mater. 2008, 18, 499. doi: 10.1002/(ISSN)1616-3028
6. [6]
  Lin, C. H.; Chang, Y. Y.; Hung, J. Y.; Lin, C. Y.; Chi, Y.; Chung, M. W.; Lin, C. L.; Chou, P. T.; Lee, G. H.; Chang, C. H.; Lin, W. C. Angew. Chem., Int. Ed. 2011, 50, 3182. doi: 10.1002/anie.201005624
7. [7]
  Kim, J. B.; Han, S. H.; Yang, K.; Kwon, S. K.; Kim, J. J.; Kim, Y. H. Chem. Commun. 2015, 51, 58. doi: 10.1039/C4CC07768G
8. [8]
  Wang, F. F.; Tao, Y. T.; Huang, W. Acta Chim. Sinica 2015, 73, 9. doi: 10.6023/A14100716
9. [9]
  Hudson, Z. M.; Sun, C.; Helander, M. G.; Chang, Y. L.; Lu, Z. H.; Wang, S. J. Am. Chem. Soc. 2012, 134, 13930. doi: 10.1021/ja3048656
10. [10]
  Wang, X.; Chang, Y. L.; Lu, J. S.; Zhang, T.; Lu, Z. H.; Wang, S. Adv. Funct. Mater. 2014, 24, 1911. doi: 10.1002/adfm.v24.13
11. [11]
  Lu, J. S.; Ko, S. B.; Walters, N. R.; Kang, Y. J.; Sauriol, F.; Wang, S. Angew. Chem., Int. Ed. 2013, 52, 4544. doi: 10.1002/anie.201300873
12. [12]
  Yang, X. L.; Sun, N.; Dang, J. S.; Huang, Z.; Yao, C. L.; Xu, X. B.; Ho, C. L.; Zhou, G. J.; Ma, D. G.; Zhao, X.; Wong, W. Y. J. Mater. Chem. C 2013, 1, 3317. doi: 10.1039/c3tc30352g
13. [13]
  Tong, G. S.; Che, C. M. Chem.-A Eur. J. 2009, 15, 7225. doi: 10.1002/chem.200802485
14. [14]
  Nozaki, K. J. Chin. Chem. Soc. 2006, 53, 101. doi: 10.1002/jccs.v53.1
15. [15]
  Williams, J. A. G. Top. Curr. Chem. 2007, 281, 205. doi: 10.1007/978-3-540-73349-2
16. [16]
  Siddique, Z. A.; Yamanoto, Y.; Ohno, T.; Nozaki, K. Inorg. Chem. 2003, 42, 6366. doi: 10.1021/ic034412v
17. [17]
  Cao Q.; Wang J.; Tian, Z. S.; Xie Z. F. J. Comput. Chem. 2012, 33, 1038. doi: 10.1002/jcc.v33.10
18. [18]
  Fraga, S.; Axena, K. M. S.; Karwowski, J., Physical Sciences Data. Amsterdam: Handbook of Atomic Data, Elsevier, Amsterdam, 1976, p. 551.
19. [19]
  Tong, G. S. M.; Chow, P. K.; To, W. P.; Kwok, W. M.; Che, C. M. Chem.-Eur. J. 2014, 20, 6433. doi: 10.1002/chem.201304375
20. [20]
  Li, Y.; Zou, L. Y.; Ren, A. M.; Ma, M. S.; Fan, J. X. Chem.-Eur. J. 2014, 20, 4671. doi: 10.1002/chem.v20.16
21. [21]
  Wang, L.; Wu, Y.; Shan, G. G.; Geng, Y.; Zhang, J. Z.; Wang, D. M.; Yang, G. C.; Su, Z. M. J. Mater. Chem. C 2014, 2, 2859. doi: 10.1039/c3tc31831a
22. [22]
  Wu, Y.; Shan, G. G.; Li, H. B.; Wu, S. X.; Ren, X. Y.; Geng, Y.; Su, Z. M. Phys. Chem. Chem. Phys. 2015, 17, 2438. doi: 10.1039/C4CP04919E
23. [23]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Nakajima, M. T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Jr., Peralta, J. E.; Ogliaro, F.; Bearpark, M, Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A.02, Gaussian, Inc., Wallingford CT, 2009.
24. [24]
  Shi, Q. H.; Peng, Q.; Sun, S. R.; Shuai, Z. G. Acta Chim. Sinica 2013, 71, 884. doi: 10.6023/A13010113
25. [25]
  Ma, M. S; Zou, L. Y.; Li, Y.; Ren, A. M.; Feng, J. K. Org. Electron. 2015, 22, 180. doi: 10.1016/j.orgel.2015.03.037
26. [26]
  Zhang, J. P.; Jin, L.; Zhang, H. X. Acta Phys.-Chim. Sin. 2011, 27, 1089.
27. [27]
  Zhang, J. P.; Jin, L.; Zhang, H. X.; Bai, F. Q. Chem. J. Chin. Univ. 2011, 32, 2885.
28. [28]
  Li, Z. D.; Suo, B. B.; Zhang, Y.; Xiao, Y. L.; Liu, W. J. Mol. Phys. 2013, 111, 3741. doi: 10.1080/00268976.2013.785611
29. [29]
  Li, Z. D.; Xiao, Y. L.; Liu, W. J. J. Chem. Phys. 2014, 137, 154114.
30. [30]
  Li, Z. D.; Liu, W. J. J. Chem. Phys. 2014, 141, 014110. doi: 10.1063/1.4885817
31. [31]
  You, Y.; Park, S. Y. Dalton Trans. 2009, 8, 1267.
32. [32]
  Zhu, R.; Lin, J.; Wen, G. A.; Liu, S. J.; Wan, J. H.; Feng, J. C.; Fan, Q. L.; Zhong, G. Y.; Wei, W.; Huang, W. Chem. Lett. 2005, 34, 1668. doi: 10.1246/cl.2005.1668
33. [33]
  Uoyamal, H.; Goushi, K.; Shizu1, K.; Nomura1, H.; Adachi, C. Nature 2012, 492, 234. doi: 10.1038/nature11687
34. [34]
  Yao, L.; Zhang, S. T.; Wang, R.; Li, W. J.; Shen, F. Z.; Yang, B.; Ma, Y. G. Angew. Chem., Int. Ed. 2014, 53, 2119. doi: 10.1002/anie.201308486
35. [35]
  Li, W. J. Y.; Pan, Y.; Xiao, R.; Peng, Q. M.; Zhang, S. T.; Ma, D. G.; Li, F.; Shen, F. Z.; Wang, Y. H.; Yang, B.; Ma, Y. G. Adv. Funct. Mater. 2014, 24, 1609. doi: 10.1002/adfm.v24.11
1. [1]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
2. [2]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
3. [3]
  Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu . Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(10): 2310034-. doi: 10.3866/PKU.WHXB202310034
4. [4]
  Juntao Yan , Liang Wei . 2D S-Scheme Heterojunction Photocatalyst. Acta Physico-Chimica Sinica, 2024, 40(10): 2312024-. doi: 10.3866/PKU.WHXB202312024
5. [5]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276
6. [6]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
7. [7]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
8. [8]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
9. [9]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
10. [10]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
11. [11]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
12. [12]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
13. [13]
  Fan JIA , Wenbao XU , Fangbin LIU , Haihua ZHANG , Hongbing FU . Synthesis and electroluminescence properties of Mn²⁺ doped quasi-two-dimensional perovskites (PEA)₂Pb_yMn_1-yBr₄. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1114-1122. doi: 10.11862/CJIC.20230473
14. [14]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(676)
HTML views(69)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Theoretical Studies on Photophysical Properties of Isomeric Iridium(Ⅲ) Complexes Ir(ppy)2(acac) Containing Dimesitylboron Moiety

Metrics

通讯作者: 陈斌, bchen63@163.com

Theoretical Studies on Photophysical Properties of Isomeric Iridium(Ⅲ) Complexes Ir(ppy)₂(acac) Containing Dimesitylboron Moiety