Citation: Gao-Nan Li, Cheng-Wei Gao, Hui Xie, Hao-Hua Chen, Dong Liu, Wei Sun, Guang-Ying Chen, Zhi-Gang Niu. New luminescent cyclometalated iridium(III) complexes containing fluorinated phenylisoquinoline-based ligands:Synthesis, structures, photophysical properties and DFT calculations[J]. Chinese Chemical Letters, ;2016, 27(03): 428-432. doi: 10.1016/j.cclet.2015.12.007 shu

New luminescent cyclometalated iridium(III) complexes containing fluorinated phenylisoquinoline-based ligands:Synthesis, structures, photophysical properties and DFT calculations

Gao-Nan Li ^a,c ,
Cheng-Wei Gao ^a ,
Hui Xie ^a ,
Hao-Hua Chen ^a ,
Dong Liu ^a ,
Wei Sun ^a ,
Guang-Ying Chen ^b ,
Zhi-Gang Niu ^a,b,c,,

a.
a. College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, China;
b.
b. Key Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education, Hainan Normal University, Haikou 571158, China;
c.
c. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China

Corresponding author: Zhi-Gang Niu,
Received Date: 21 October 2015
Available Online: 11 November 2015
Fund Project: This work was supported by the National Natural Science Foundation of China (No.21501037) (No.21501037) the Natural Science Foundation of Hainan Province (No.20152017) (No.20152017)

Two new fluorinated phenylisoquinoline-based iridium(Ⅲ) complexes,[Ir(f₂piq)₂(bipy)] [PF₆] (3a) and[Ir(fmpiq)₂(bipy)] [PF₆] (3b) (f₂piq=1-(2,4-difluorophenyl)isoquinoline, fmpiq=1-(4-fluoro-2-methylphenyl) isoquinoline, bipy=2,2'-bipyridine), have been synthesized and fully characterized. Single crystal X-ray diffraction study has been undertaken on complexes 3a and 3b, which show that each adopts the distorted octahedral coordination geometry with the cis-C,C' and trans-N,N' configuration. The photoluminescence spectra of 3a and 3b exhibit yellow and orange emission maxima at 584 and 600 nm, respectively. The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 3a-3b have been calculated with density functional theory (DFT) and time-dependent DFT (TD-DFT). The absorption and emission spectra of complex 3b is red-shifted relative to those of complex 3a, as a consequence of the nature of the methyl group.
- Iridium(III) complex,
- Phenylisoquinoline,
- Crystal structure,
- Photoluminescence,
- DFT calculation
1. [1]
  [1] M.A. Baldo, D.F. O'Brien, Y. You, et al., Highly emission from electroluminescent phosphorescent organic devices, Nature 395(1998) 151-154.
2. [2]
  [2] M.A. Baldo, S. Lamansky, P.E. Burrows, et al., Very high-efficiency green organic light-emitting devices based on electrophosphorescence, Appl. Phys. Lett. 75(1999) 4-6.
3. [3]
  [3] M.A. Baldo, C. Adachi, S.R. Forrest, et al., High-efficiency organic electrophosphorescent devices with tris(2-phenylpyridine)iridium doped into electrontransporting materials, Appl. Phys. Lett. 77(2000) 904-906.
4. [4]
  [4] S. Lamansky, P. Djurovich, D. Murphy, et al., Synthesis and characterization of phosphorescent cyclometalated iridium complexes, (Ⅰ)norg. Chem. 40(2001) 1704-1711.
5. [5]
  [5] N.G. Park, M.Y. Kwak, B.O. Kim, et al. Jpn. J. Appl. Phys. 41(2002) 1523-1526.
6. [6]
  [6] A.B. Tamayo, B.D. Alleyne, P.(Ⅰ). Djurovich, et al., Synthesis and characterization of facial and meridional tris-cyclometalated iridium(Ⅲ) complexes, J. Am. Chem. Soc. 125(2003) 7377-7387.
7. [7]
  [7] W.Y. Wong, C.L. Ho, Z.Q. Gao, et al., Multifunctional iridium complexes based on carbazole modules as highly efficient electrophosphores, Angew. Chem. (Ⅰ)nt. Ed. 45(2006) 7800-7803.
8. [8]
  [8] H.H. Chou, C.H. Cheng, A highly efficient universal bipolar host for blue, green, and red phosphorescent OLEDs, Adv. Mater. 22(2010) 2468-2471.
9. [9]
  [9] Y.T. Tao, Q.A. Wang, C.L. Yang, et al., Multifunctional triphenylamine/oxadiazole hybrid as host and exciton-blocking material:high efficiency green phosphorescent OLEDs using easily available and common materials, Adv. Funct. Mater. 20(2010) 2923-2929.
10. [10]
  [10] D. Sykes, (Ⅰ).S. Tidmarsh, A. Barbieri, et al., d→f energy transfer in a series of (Ⅰ)r(Ⅲ)/Eu(Ⅲ) dyads:energy-transfer mechanisms and white-light emission, (Ⅰ)norg. Chem. 50(2011) 11323-11339.
11. [11]
  [11] Y. Zheng, A.S. Batsanov, R.M. Edkins, et al., Thermally induced defluorination during a mer to fac transformation of a blue-green phosphorescent cyclometalated iridium(Ⅲ) complex, (Ⅰ)norg. Chem. 51(2012) 290-297.
12. [12]
  [12] C.L. Ho, W.Y. Wong, Q. Wang, et al., A multifunctional iridium-carbazolyl orange phosphor for high-performance two-element WOLED exploiting excitonmanaged fluorescence/phosphorescence, Adv. Funct. Mater. 18(2008) 928-937.
13. [13]
  [13] F. Babudri, G.M. Farinola, F. Naso, et al., Fluorinated materials for electronic and optoelectronic applications:the role of the fluorine atom, Chem. Commun. (2007) 1003-1022.
14. [14]
  [14] Z.G. Niu, D. Liu, J. Zuo, et al., Four new cyclometalated phenylisoquinoline-based (Ⅰ)r(Ⅲ) complexes:syntheses, structures, properties and DFT calculations, (Ⅰ)norg. Chem. Commun. 43(2014) 146-150.
15. [15]
  [15] Agilent Technologies (Ⅰ)nc., CrysAlisPro Version 1.171.36.21, Agilent Technologies (Ⅰ)nc., Santa Clara, CA, USA, 2012.
16. [16]
  [16] G.M. Sheldrick, A short history of shelx, Acta Crystallogr. Sect. A:Found. Crystallogr. 64(2008) 112-122.
17. [17]
  [17] O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, et al., Olex2:a complete structure solution, refinement and analysis program, J. Appl. Cryst. 42(2009) 339-341.
18. [18]
  [18] A.L. Spek, Single-crystal structure validation with the program platon, J. Appl. Crystallogr. 36(2003) 7-13.
19. [19]
  [19] P.V.D. Sluis, A.L. Spek, Bypass:an effective method for the refinement of crystal structures containing disordered solvent regions, Acta Crystallogr. Sect. A:Found. Crystallogr. 46(1990) 194-201.
20. [20]
  [20] M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al., Gaussian 09, Revision A. 01, Gaussian, (Ⅰ)nc, Wallingford, CT, 2009.
21. [21]
  [21] C. Lee, W. Yang, R.G. Parr, Development of the colle-salvetti correlation-energy formula into a functional of the electron density, Phys. Rev. B:Condens. Matter 37(1988) 785-789.
22. [22]
  [22] B. Miehlich, A. Savin, H. Stoll, et al., Results obtained with the correlation energy density functionals of becke and lee, yang and parr, Chem. Phys. Lett. 157(1989) 200-206.
23. [23]
  [23] A.D. Becke, Density-functional thermochemistry. Ⅲ. The role of exact exchange, J. Chem. Phys. 98(1993) 5648-5652.
24. [24]
  [24] M. Cossi, N. Rega, G. Scalmani, et al., Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model, J. Comput. Chem. 24(2003) 669-681.
25. [25]
  [25] J. Tomasi, B. Mennucci, R. Cammi, Quantum mechanical continuum solvation models, Chem. Rev. 105(2005) 2999-3093.
26. [26]
  [26] A. Juris, V. Balzani, F. Barigelletti, et al., Ru(Ⅱ) polypyridine complexes:photophysics, photochemistry, electrochemistry, and chemiluminescence, Coord. Chem. Rev. 84(1988) 85-227.
27. [27]
  [27] M. Frank, M. Nieger, F. Vögtle, et al., Dinuclear Ru^Ⅱ and/or Os^Ⅱ complexes of bis, (Ⅰ)norg. Chim. Acta. 242(1996) 281-291.
28. [28]
  [28] K.A. King, P.J. Spellane, R.J. Watts, Excited-state properties of a triply orthometalated iridium(Ⅲ) complex, J. Am. Chem. Soc. 107(1985) 1431-1432.
29. [29]
  [29] S. Kammer, (Ⅰ). Starke, A. Pietrucha, et al., 1,12-diazaperylene and 2,11-dialkylated-1,12, Dalton Trans. 41(2012) 10219-10227.
30. [30]
  [30] M. Bandini, M. Bianchi, G. Valenti, et al., Electrochemiluminescent functionalizable cyclometalated thiophene-based iridium(Ⅲ) complexes, (Ⅰ)norg. Chem. 49(2010) 1439-1448.
31. [31]
  [31] S.K. Leung, K.Y. Kwok, K.Y. Zhang, et al., Design of luminescent biotinylation reagents derived from cyclometalated iridium(Ⅲ) and rhodium(Ⅲ) bis(pyridylbenzaldehyde) complexes, (Ⅰ)norg. Chem. 49(2010) 4984-4995.
32. [32]
  [32] T. Hofbeck, H. Yersin, The triplet state of fac-(Ⅰ)r(ppy)₃, (Ⅰ)norg. Chem. 49(2010) 9290-9299.
33. [33]
  [33] Q.L. Xu, C.C. Wang, T.Y. Li, et al., Syntheses, photoluminescence, and electroluminescence of a series of iridium complexes with trifluoromethyl-substituted 2-phenylpyridine as the main ligands and tetraphenylimidodiphosphinate as the ancillary ligand, (Ⅰ)norg. Chem. 52(2013) 4916-4925.
34. [34]
  [34] M. Tavasli, T.N. Moore, Y.H. Zheng, et al., Colour tuning from green to red by substituent effects in phosphorescent tris-cyclometalated iridium(Ⅲ) complexes of carbazole-based ligands:synthetic, photophysical, computational and high efficiency OLED studies, J. Mater. Chem. 22(2012) 6419-6428.
35. [35]
  [35] K.R.J. Thomas, M. Velusamy, J.T. Lin, et al., Efficient red-emitting cyclometalated iridium(Ⅲ) complexes containing lepidine-based ligands, (Ⅰ)norg. Chem. 44(2005) 5677-5685.
36. [36]
  [36] M.S. Lowry, W.R. Hudson, R.A. Pascal Jr., et al., Accelerated luminophore discovery through combinatorial synthesis, J. Am. Chem. Soc. 126(2004) 14129-14135.
37. [37]
  [37] Q. Zhao, S.J. Liu, M. Shi, et al., Series of new cationic iridium(Ⅲ) complexes with tunable emission wavelength and excited state properties:structures, theoretical calculations, and photophysical and electrochemical properties, (Ⅰ)norg. Chem. 45(2006) 6152-6160.
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