Room-Temperature Phosphorescence from a Series of 3-Pyridylcarbazole Derivatives.

Abstract

Exploration of pure metal-free organic molecules that exhibit strong room-temperature phosphorescence (RTP) is an emerging research topic. In this regard, unveiling the design principles for an efficient RTP molecule is an essential but challenging task. A small molecule is an ideal platform to precisely understand the fundamental role of each functional component because the parent molecule can be easily derivatized. Here, the RTP behaviors of a series of 3-pyridylcarbazole derivatives are presented. Experimental studies in combination with theoretical calculations reveal the crucial role of the n orbital on the central pyridine ring in the dramatic enhancement of the intersystem crossing between the charge-transfer-excited singlet state and the locally excited triplet states. Single crystal X-ray crystallographic studies apparently indicate that both the pyridine ring and fluorine atom contribute to the enhancement of the RTP because of the restricted motion owing to weak CH-N and H-F hydrogen-bonding interactions. The single crystal of the fluorine-substituted derivative shows an ultra-long phosphorescent lifetime ( τ P ) of 1.1 s and a phosphorescence quantum yield ( Φ P ) of 1.2%, while the bromine-substituted derivative exhibits τ P of 0.15 s with a Φ P of 7.9%. We believe that this work provides a fundamental and universal guideline for the generation of pure organic molecules exhibiting strong RTP.