Side group dependent room temperature crystallization-induced phosphorescence of benzil based all organic phosphors

Abstract

In this work, we report alkoxy substituted benzil based all organic room temperature phosphors which showed crystallization induced phosphorescence (CIP). Nine title compounds were prepared with various alkyl lengths (OC_nH_2n+1: n = 8–16) and the effect of alkyl side group length on the phosphorescence performance was investigated, as compared to p-anisil. It was found that both phosphorescence quantum yield and lifetime increased concomitantly as the alkyl length increased up to nonyloxy (BZL-OC9). Further increase in the carbon number caused the phosphorescence performance to deteriorate due to greater conformational freedom of the side groups. An incredible quantum yield of 70% was achieved for BZL-OC9. A promising finding is that the increased quantum yield was accompanied by the increase in the lifetime relative to p-anisil, which has been historically challenging. Single crystallography coupled with UV-Vis spectroscopy revealed that a higher level of intermolecular π–π interactions was observed from p-anisil while more alkyl interactions with less intermolecular π-orbital overlap were found for BZL-OC8. As a result, molecular rigidification with less phosphorescence quenching was achieved for BZL-OC8 leading to enhanced performance. A precipitation study on a dichloromethane solution as a function of the content of MeOH (poor solvent) proved that the emission of the BZL-OCn system is truly aggregation-induced. The current work demonstrates that strategic side group engineering could be a promising approach to developing high-performance all organic phosphors as well as improving the properties of existing phosphors.