DFT and TD-DFT study on the electronic structures and phosphorescent properties of a series of heteroleptic iridium(III) complexes

Xiaohong Shang, Deming Han, Qing Zhan, Gang Zhang, Dongfeng Li

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The electronic structures and phosphorescent properties of a series of heteroleptic iridium(III) complexes (mpmi)2Ir(dmpypz) (1; mpmi = 1-(4-tolyl)-3-methylimidazolium, dmpypz = 3,5-dimethyl-2-(pyrazol-3-yl)pyridine) , (bpmi)2Ir(dmpypz) (2; bpmi = 1-biphenyl-4-yl-3-methylimidazole), (dfmi)2Ir(dmpypz) (3; dfmi = 1-(2,6-difluorobiphenyl)-3- methylimidazole), (mtmi)2Ir(dmpypz) (4; mtmi = 1-methyl-3-(4′- (trifluoromethyl)biphenyl-4-yl)imidazole), (fmmi)2Ir(dmpypz) (5; fmmi = 1-(fluoren-2-yl)-3-methylimidazole), and (mhmi)2Ir(dmpypz) (6; mhmi = 1-methyl-3-phenanthren-2-ylimidazole) have been investigated by using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The influence of different substituent groups and π-conjugation degrees on the optical and electronic properties of Ir(III) complexes was also explored by introducing phenyl, fluorophenyl, (trifluoromethyl)phenyl, and rigid construction on the phenylimidazole moiety of a cyclometalated ligand (ĈC) in complex 1. The calculated results show that the lowest energy absorption wavelengths of complexes 1-6 are 387, 380, 378, 375, 391, and 384 nm, respectively. The introduction of different substituent groups leads to different degrees of red shift for complexes 2-6 in emission spectra in comparison with that of complex 1. It is believed that the highest triplet metal to ligand charge transfer 3MLCT (%) contribution, smallest ΔES1-T1 and higher μS1 values, and larger 3MC-3MLCT energy gap for 3 ensure its higher quantum yield in comparison with that of other complexes.

Original languageEnglish (US)
Pages (from-to)3300-3308
Number of pages9
JournalOrganometallics
Volume33
Issue number13
DOIs
StatePublished - Jul 14 2014

Fingerprint

Iridium
iridium
Electronic structure
Density functional theory
density functional theory
electronic structure
Ligands
ligands
energy absorption
Energy absorption
Quantum yield
conjugation
imidazoles
Electronic properties
red shift
Charge transfer
pyridines
emission spectra
Energy gap
Optical properties

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Shang, Xiaohong ; Han, Deming ; Zhan, Qing ; Zhang, Gang ; Li, Dongfeng. / DFT and TD-DFT study on the electronic structures and phosphorescent properties of a series of heteroleptic iridium(III) complexes. In: Organometallics. 2014 ; Vol. 33, No. 13. pp. 3300-3308.
@article{a4481d615cdd45f9a6213d1bca26f15a,
title = "DFT and TD-DFT study on the electronic structures and phosphorescent properties of a series of heteroleptic iridium(III) complexes",
abstract = "The electronic structures and phosphorescent properties of a series of heteroleptic iridium(III) complexes (mpmi)2Ir(dmpypz) (1; mpmi = 1-(4-tolyl)-3-methylimidazolium, dmpypz = 3,5-dimethyl-2-(pyrazol-3-yl)pyridine) , (bpmi)2Ir(dmpypz) (2; bpmi = 1-biphenyl-4-yl-3-methylimidazole), (dfmi)2Ir(dmpypz) (3; dfmi = 1-(2,6-difluorobiphenyl)-3- methylimidazole), (mtmi)2Ir(dmpypz) (4; mtmi = 1-methyl-3-(4′- (trifluoromethyl)biphenyl-4-yl)imidazole), (fmmi)2Ir(dmpypz) (5; fmmi = 1-(fluoren-2-yl)-3-methylimidazole), and (mhmi)2Ir(dmpypz) (6; mhmi = 1-methyl-3-phenanthren-2-ylimidazole) have been investigated by using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The influence of different substituent groups and π-conjugation degrees on the optical and electronic properties of Ir(III) complexes was also explored by introducing phenyl, fluorophenyl, (trifluoromethyl)phenyl, and rigid construction on the phenylimidazole moiety of a cyclometalated ligand (ĈC) in complex 1. The calculated results show that the lowest energy absorption wavelengths of complexes 1-6 are 387, 380, 378, 375, 391, and 384 nm, respectively. The introduction of different substituent groups leads to different degrees of red shift for complexes 2-6 in emission spectra in comparison with that of complex 1. It is believed that the highest triplet metal to ligand charge transfer 3MLCT ({\%}) contribution, smallest ΔES1-T1 and higher μS1 values, and larger 3MC-3MLCT energy gap for 3 ensure its higher quantum yield in comparison with that of other complexes.",
author = "Xiaohong Shang and Deming Han and Qing Zhan and Gang Zhang and Dongfeng Li",
year = "2014",
month = "7",
day = "14",
doi = "10.1021/om401194z",
language = "English (US)",
volume = "33",
pages = "3300--3308",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "13",

}

DFT and TD-DFT study on the electronic structures and phosphorescent properties of a series of heteroleptic iridium(III) complexes. / Shang, Xiaohong; Han, Deming; Zhan, Qing; Zhang, Gang; Li, Dongfeng.

In: Organometallics, Vol. 33, No. 13, 14.07.2014, p. 3300-3308.

Research output: Contribution to journalArticle

TY - JOUR

T1 - DFT and TD-DFT study on the electronic structures and phosphorescent properties of a series of heteroleptic iridium(III) complexes

AU - Shang, Xiaohong

AU - Han, Deming

AU - Zhan, Qing

AU - Zhang, Gang

AU - Li, Dongfeng

PY - 2014/7/14

Y1 - 2014/7/14

N2 - The electronic structures and phosphorescent properties of a series of heteroleptic iridium(III) complexes (mpmi)2Ir(dmpypz) (1; mpmi = 1-(4-tolyl)-3-methylimidazolium, dmpypz = 3,5-dimethyl-2-(pyrazol-3-yl)pyridine) , (bpmi)2Ir(dmpypz) (2; bpmi = 1-biphenyl-4-yl-3-methylimidazole), (dfmi)2Ir(dmpypz) (3; dfmi = 1-(2,6-difluorobiphenyl)-3- methylimidazole), (mtmi)2Ir(dmpypz) (4; mtmi = 1-methyl-3-(4′- (trifluoromethyl)biphenyl-4-yl)imidazole), (fmmi)2Ir(dmpypz) (5; fmmi = 1-(fluoren-2-yl)-3-methylimidazole), and (mhmi)2Ir(dmpypz) (6; mhmi = 1-methyl-3-phenanthren-2-ylimidazole) have been investigated by using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The influence of different substituent groups and π-conjugation degrees on the optical and electronic properties of Ir(III) complexes was also explored by introducing phenyl, fluorophenyl, (trifluoromethyl)phenyl, and rigid construction on the phenylimidazole moiety of a cyclometalated ligand (ĈC) in complex 1. The calculated results show that the lowest energy absorption wavelengths of complexes 1-6 are 387, 380, 378, 375, 391, and 384 nm, respectively. The introduction of different substituent groups leads to different degrees of red shift for complexes 2-6 in emission spectra in comparison with that of complex 1. It is believed that the highest triplet metal to ligand charge transfer 3MLCT (%) contribution, smallest ΔES1-T1 and higher μS1 values, and larger 3MC-3MLCT energy gap for 3 ensure its higher quantum yield in comparison with that of other complexes.

AB - The electronic structures and phosphorescent properties of a series of heteroleptic iridium(III) complexes (mpmi)2Ir(dmpypz) (1; mpmi = 1-(4-tolyl)-3-methylimidazolium, dmpypz = 3,5-dimethyl-2-(pyrazol-3-yl)pyridine) , (bpmi)2Ir(dmpypz) (2; bpmi = 1-biphenyl-4-yl-3-methylimidazole), (dfmi)2Ir(dmpypz) (3; dfmi = 1-(2,6-difluorobiphenyl)-3- methylimidazole), (mtmi)2Ir(dmpypz) (4; mtmi = 1-methyl-3-(4′- (trifluoromethyl)biphenyl-4-yl)imidazole), (fmmi)2Ir(dmpypz) (5; fmmi = 1-(fluoren-2-yl)-3-methylimidazole), and (mhmi)2Ir(dmpypz) (6; mhmi = 1-methyl-3-phenanthren-2-ylimidazole) have been investigated by using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The influence of different substituent groups and π-conjugation degrees on the optical and electronic properties of Ir(III) complexes was also explored by introducing phenyl, fluorophenyl, (trifluoromethyl)phenyl, and rigid construction on the phenylimidazole moiety of a cyclometalated ligand (ĈC) in complex 1. The calculated results show that the lowest energy absorption wavelengths of complexes 1-6 are 387, 380, 378, 375, 391, and 384 nm, respectively. The introduction of different substituent groups leads to different degrees of red shift for complexes 2-6 in emission spectra in comparison with that of complex 1. It is believed that the highest triplet metal to ligand charge transfer 3MLCT (%) contribution, smallest ΔES1-T1 and higher μS1 values, and larger 3MC-3MLCT energy gap for 3 ensure its higher quantum yield in comparison with that of other complexes.

UR - http://www.scopus.com/inward/record.url?scp=84904283599&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84904283599&partnerID=8YFLogxK

U2 - 10.1021/om401194z

DO - 10.1021/om401194z

M3 - Article

AN - SCOPUS:84904283599

VL - 33

SP - 3300

EP - 3308

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 13

ER -