Modulation of iridium(III) phosphorescence via photochromic ligands : a density functional theory study

• The photochromic iridium(III) complex (Py-BTE)(2)Ir(acac) synthesized by Tan et al. [W. Tan et al., Org. Lett. 2009, 11, 161-164] has shown distinct photo-reactivity and photo-controllable phosphorescence. We here present a density functional theory study on the (Py-BTE)(2)Ir(acac) complex to explore the mechanism at the molecular level and to help further design of photochromic iridium(III) complexes with the desirable properties. The hybrid functional PBE0, with 25% Hartree-Fock exchange, is found to give an optimal structure compared with X-ray crystallographic data. The absorption bands are well reproduced by using time-dependent density functional theory calculations, lending the possibility to assign the metal-to-ligand and intra-ligand charge transfer transitions. The radiative and nonradiative deactivation rate constants, k(r) and k(nr), are rationalized for both the open-ring and closed-ring forms of the complex. The very large k(nr) and small k(r) make the closed-ring form of the complex non-emissive. The triplet reactivity of the Py-BTE ligand is also studied by performing density functional theory calculations on the potential energy surfaces of the ground state and the lowest triplet state.

Subject headings

NATURVETENSKAP  -- Kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

Keyword

EFFECTIVE CORE POTENTIALS

CONTAINING 1

10-PHENANTHROLINE LIGAND

AB-INITIO

SPECTROSCOPIC PROPERTIES

MOLECULAR CALCULATIONS

IR(III) COMPLEXES

ELECTROLUMINESCENT DEVICES

PHOTOPHYSICAL PROPERTIES

EXCITATION-ENERGIES

RHENIUM(I) COMPLEX

Chemistry

Kemi

Chemistry

Publication and Content Type

ref (subject category)

art (subject category)