330
J Fluoresc (2016) 26:323–331
8. Li YF, Liu Y, Zhou M (2012) Acid induced acetylacetonato replace-
ment in biscyclometalated iridium(III) complexes. Dalton Trans 41:
3807–3816
9. Hay PJ (2002) Theoretical studies of the ground and excited
electronic states in cyclometalated phenylpyridine Ir(III) com-
plexes using density functional theory. J Phys Chem A 106:
1634–1641
have an almost equal HOMO value, and 3c has the highest
one of all. This again demonstrate that the replacement of O
by S at para-position of coordinated N atom slightly influence
the HOMO energy levels, whereas the substitution of C by N
in adjacent position can improve them effectively.
10. Tamayo AB, Alleyne BD, Djurovich PI, Lamansky S, Tsyba I, Ho
NN, Bau R, Thompson ME (2003) Synthesis and characterization
of facial and meridional tris-cyclometalated iridium(III) complexes.
J Am Chem Soc 125:7377–7387
Conclusion
11. Sharma S, Kim H, Lee YH, Kim T, Lee YS, Lee MH (2014)
Heteroleptic cyclometalated iridium(III) complexes supported by
triarylborylpicolinate ligand: ratiometric turn-on phosphorescence
response upon fluoride binding. Inorg Chem 53:8672–8680
12. Li GN, Zou Y, Yang YD, Liang J, Cui F, Zheng T, Xie H, Niu ZG
(2014) Deep-red phosphorescent iridium(III) complexes containing
1-(benzo[b] thiophen-2-yl) isoquinoline ligand: synthesis,
photophysical and electrochemical properties and DFTcalculations.
J Fluoresc 24:1545–1552
13. Juris A, Balzani V, Barigelletti F, Campagna S, Belser P, Vonzelewsky
A (1988) Ru(II) polypyridine complexes: photophysics, photochem-
istry, eletrochemistry, and chemiluminescence. Coord Chem Rev 84:
85–277
14. Frank M, Nieger M, Vögtle F, Belser P, Vonzelewsky A, Cola LD,
Balzani V, Barigelletti F, Flamigni L (1996) Dinuclear RuII and/or
OsII complexes of bis-bipyridine bridging ligands containing
adamantane spacers: synthesis, luminescence properties,
intercomponent energy and electron transfer processes. Inorg
Chim Acta 242:281–291
15. Oh H, Park KM, Hwang H, Oh S, Lee JH, Lu JS, Wang S, Kang Y
(2013) Effective alkoxylation of phosphorescent heteroleptic
iridium(III) compounds bearing fluorinated bipyridine ligands.
Organometallics 32:6427–6436
In conclusion, we have synthesized and characterized three
new cyclometalated [(btp)2Ir(LX)] iridium(III) complexes
3a − 3c (LX = bozp, btzp and izp). The effects of three differ-
ent ancillary ligands on photophysical and electrochemical
properties were studied. Each Ir(III) complex exhibits a max-
imum main peak and a shoulder peak in emission spectra,
which is suggested to be a mixiture of ligand-centered
(3π-π*) and 3MLCT excited states. Further, analyses of DFT
and TD-DFT calculations indicate that the lowest-energy elec-
tronic transitions are attributed to MLCT and LLCT π → π*
transition.
Acknowledgments This work was supported by the National Natural
Science Foundation of China (No. 21501037), the Natural Science Foun-
dation of Hainan Province (No. 20152017), the Science and Research
Project of Education Department of Hainan Province (Nos. Hjkj2013-
25 and Hnky2015-27) and Hainan Normal University’s Innovation Ex-
periment Program for University Students (No. cxcyxj2015005).
16. CrysAlisPro Version 1.171.36.21. (2012) Agilent technologies Inc.
Santa Clara, CA
17. Sheldrick GM (2008) A short history of SHELX. Acta Cryst Sect A
64:112–122
References
1. Baldo MA, Adachi C, Forrest SR (2000) Transient analysis of or-
ganic electrophosphorescence. II. Transientanalysis of triplet-triplet
annihilation. Phys Rev B 62:10967–10977
18. Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JK, Puschmann H
(2009) OLEX2: a complete structure solution, refinement and anal-
ysis program. J Appl Crystallogr 42:339–341
2. Wu C, Chen HF, Wong KT, Thompson ME (2010) Study of ion-
paired iridium complexes (soft salts) and their application in organ-
ic light emitting diodes. J Am Chem Soc 132:3133–3139
3. Lupton JM, Samuel IDW, Frampton MJ, Beavington R, Burn PL
(2001) Control of electrophosphorescence in conjugated dendrimer
light-emitting diodes. Adv Funct Mater 11:287–294
4. Niu ZG, Liu D, Zuo J, Zou Y, Yang JM, Su YH, Yang YD, Li GN
(2014) Four new cyclometalated phenylisoquinoline-based Ir(III)
complexes: syntheses, structures, properties and DFT calculations.
Inorg Chem Commun 43:146–150
5. Lamansky S, Djurovich P, Murphy D, Abdel-Razzaq F, Lee HE,
Adachi C, Burrows PE, Forrest SR, Thompson ME (2001) Highly
phosphorescent bis-cyclometalated iridium complexes: synthesis,
photophysical characterization, and use in organic light emitting
diodes. J Am Chem Soc 123:4304–4312
6. Chen LQ, Yang CL, Qin JG, Gao J, Ma DG (2006) Tuning of
emission: synthesis, structure and photophysical properties of im-
idazole, oxazole and thiazole-based iridium (III) complexes. Inorg
Chim Acta 359:4207–4214
19. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA,
Cheeseman JR, Montgomery JA, Vreven T, Kudin KN, Burant
JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B,
Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada
M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima
T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian
HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE,
Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala
PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ,
Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O,
Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV,
Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G,
Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T,
Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill
PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA
(2009) Gaussian 09, Revision A.01. Wallingford, Gaussian, Inc.
20. Lee C, Yang W, Parr RG (1988) Development of the colle-salvetti
correlation-energy formula into a functional of the electron density.
Phys Rev B 37:785–789
21. Miehlich B, Savin A, Stoll H, Preuss H (1989) Results obtained
with the correlation energy density functionals of becke and Lee,
Yang and Parr. Chem Phys Lett 157:200–206
22. Becke AD (1993) Density-functional thermochemistry.III. The role
of exact exchange. J Chem Phys 98:5648–5652
7. Zhao Q, Jiang CY, Shi M, Li FY, Yi T, Cao Y, Huang CH (2006)
Synthesis and photophysical, electrochemical, and
electrophosphorescent properties of a series of iridium(III) com-
plexes based on quinoline derivatives and different β-diketonate
ligands. Organometallics 25:3631–3638