Effects of intramolecular hydrogen bonds on phosphorescence emission: A theoretical perspective

Abstract

Importing intramolecular hydrogen bond in phosphorescent transition metal complexes has been considered one of the excellent approaches to improve the electroluminescence performance of organic light‐emitting diodes in real applications. However, the relationships between such H‐bond structure and phosphorescent properties have not been theoretically revealed yet. In this study, two types of intramolecular hydrogen bonds are introduced into the two classes of traditional materials, that is, Pt(II) and Ir(III) complexes (1a and 2a) to completely elucidate their influence on the structures and properties by comparing with the original phosphors (1b and 2b) using density functional theory/time‐dependent density functional theory for the first time. A comprehensive analysis of the geometric structures, molecular orbitals, and luminescence properties (including phosphorescence emission wavelengths and radiative and nonradiative decay processes) has been carried out. Our theoretical model highlights that complexes 1a and 2a embedded with H‐bonds significantly promote the phosphorescence emission band blue‐shifted and restrict molecular deformations compared with the corresponding 1b and 2b, which can provide helpful guidance to regulate and design several aspects of highly efficient blue phosphorescent emitters.