Issue 69, 2016, Issue in Progress

Spin–orbit coupling analyses of phosphorescence: the effects of cyclometalated ligand replacement in fac-Ir(ppy)3 with various bpy ligands on blue phosphorescence

Abstract

Multi-configuration self-consistent field (MCSCF) calculations followed by second-order configuration interaction (SOCI) and spin–orbit coupling (SOC) calculations were performed using one of the effective core potentials and its associated basis set, the Stevens–Basch–Krauss–Jasien–Cundari (SBKJC) basis set referred to here as SBKJC+p, in order to examine the effects of replacement of a methine group in each phenylpyridine (ppy) ligand of the facial (fac) isomer of tris(2-phenylpyridinato)iridium(III)[fac-Ir(ppy)3] by a nitrogen atom for the purpose of obtaining deep blue phosphorescence. Only replacements of the methine group at the 3′ or 5′ site of each ppy ligand by nitrogen atoms were calculated to induce a spectral shift to the blue region. These results can be explained by the strong electronegativity of nitrogen atoms and by the magnitude of the electron density at the 2′ carbon atom of the ppy or bipyridine (bpy) ligands. Subsequently, the substituent effects in the fac isomer of tris(bipyridinato)iridium(III)[fac-Ir(bpy)3] were investigated and found to be similar to those in fac-Ir(ppy)3 as reported in our previous study (RSC Adv., 2015, 5, 35760–35772). Based on systematic calculations and theoretical consideration, the most effective modification for deep blue phosphorescence should be the introduction of a nitrogen atom into the 3′ or/and 5′ site of benzene rings of the ppy ligands in fac-Ir(ppy)3 together with the combination of the substituents X = F, NR2, or OR (R = alkyl group) and Y = CN or NO2.

Graphical abstract: Spin–orbit coupling analyses of phosphorescence: the effects of cyclometalated ligand replacement in fac-Ir(ppy)3 with various bpy ligands on blue phosphorescence

Supplementary files

Article information

Article type
Paper
Submitted
25 Mar 2016
Accepted
03 Jul 2016
First published
04 Jul 2016

RSC Adv., 2016,6, 65020-65030

Spin–orbit coupling analyses of phosphorescence: the effects of cyclometalated ligand replacement in fac-Ir(ppy)3 with various bpy ligands on blue phosphorescence

H. Yoshinaga, T. Asada, S. Koseki, S. Yagi and T. Matsushita, RSC Adv., 2016, 6, 65020 DOI: 10.1039/C6RA07778A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements