An Insight of the Results Provided by Color-Tuning Studies Made on Ir(III) Complexes

A pi-Neutral CF 3 Group Viewed by Adjusting Energies of pi-type Molecular Orbitals

Hung Sung Lin, Shou Yun Lu, Fu-Yung Huang, Yan Wu, Wei Lin Su, Shao Pin Wang

Research output: Contribution to journalArticle

Abstract

The pi-nature of a CF 3 group can be understood through analysis of its bond orbitals (BOs) mixed into the pi-type molecular orbitals of CF 3 -substituted Ir(ppy) 2 MDPA + complexes (ppy=2-phenyl-pyridine and MDPA=methylated 2,2′-dipyridyl amine). It has been found that, through this natural bond orbital analysis, the parent's molecular orbitals (MOs) can be stabilized by σ∗ CF BO via negative hyperconjugation and, simultaneously, destabilized by electron lp(F) BO. Since these two competing pi-effects are virtually counterbalanced as indicated by the vanishing values of crystal orbital overlap populations, the chemical substitution strategy originated from lowering of HOMO by using this electron-withdrawing CF 3 group has been found effective in color-tuning to blue region. Based on reduced shielding effect due to de- creased σ-electron density, the reported position dependent CF 3 -substitution effects on pi-type MOs can also be understood through HOMO/LUMO wavefunction analysis.

Original languageEnglish
Pages (from-to)939-943
Number of pages5
JournalJournal of the Chinese Chemical Society
Volume62
Issue number11
DOIs
Publication statusPublished - 2015 Nov 1

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Molecular orbitals
Tuning
Color
Substitution reactions
Electrons
Wave functions
Shielding
Amines
Carrier concentration
Crystals

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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title = "An Insight of the Results Provided by Color-Tuning Studies Made on Ir(III) Complexes: A pi-Neutral CF 3 Group Viewed by Adjusting Energies of pi-type Molecular Orbitals",
abstract = "The pi-nature of a CF 3 group can be understood through analysis of its bond orbitals (BOs) mixed into the pi-type molecular orbitals of CF 3 -substituted Ir(ppy) 2 MDPA + complexes (ppy=2-phenyl-pyridine and MDPA=methylated 2,2′-dipyridyl amine). It has been found that, through this natural bond orbital analysis, the parent's molecular orbitals (MOs) can be stabilized by σ∗ CF BO via negative hyperconjugation and, simultaneously, destabilized by electron lp(F) BO. Since these two competing pi-effects are virtually counterbalanced as indicated by the vanishing values of crystal orbital overlap populations, the chemical substitution strategy originated from lowering of HOMO by using this electron-withdrawing CF 3 group has been found effective in color-tuning to blue region. Based on reduced shielding effect due to de- creased σ-electron density, the reported position dependent CF 3 -substitution effects on pi-type MOs can also be understood through HOMO/LUMO wavefunction analysis.",
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An Insight of the Results Provided by Color-Tuning Studies Made on Ir(III) Complexes : A pi-Neutral CF 3 Group Viewed by Adjusting Energies of pi-type Molecular Orbitals. / Lin, Hung Sung; Lu, Shou Yun; Huang, Fu-Yung; Wu, Yan; Su, Wei Lin; Wang, Shao Pin.

In: Journal of the Chinese Chemical Society, Vol. 62, No. 11, 01.11.2015, p. 939-943.

Research output: Contribution to journalArticle

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