Afterglows from the indolocarbazole families

• Syntheses and crystal structures of the five isomeric ICZs are completely revealed. • Organic amorphous afterglows of the indolocarbazole families are firstly presented. • ICZ- P 2 realized PLQY, afterglow lasting time and lifetime of 31.06%, 35 s and 2.32 s. • Data security applications based on the afterglows of the ICZ-PVA inks are developed. Indolocarbazoles (ICZs) and their derivates were immensely studied in the fields of organic opto-electronics, sensors and anti-cancer agents. However, the afterglow researches, the comprehensive syntheses and crystal structures of the isomeric ICZs remained shortages. Currently, the organic afterglows were mainly focused on the crystalline states, showing restrictions and inconveniences in practical applications, the organic amorphous afterglows were more favorable but were limitedly documented. Herein, the syntheses, single crystal structures, afterglow studies and data protection applications of the ICZ families with five isomers were together presented for the first time. For these ICZ crystals, the planar configurations and high void rates made them prone to stack and vulnerable to the O 2 and humidity, affected by these factors, they were hard to radiate phosphorescence at room temperature, which can be more easily aroused at 77 K. By doping the ICZ into PVA, a rigid and confined environment was built by the hydrogen bond interaction between the –NH and –OH unit in the ICZ and PVA chain, greatly hindering the molecular motion, O 2 and humidity quenchers. Consequently, the triplet states were efficiently stabilized, the nonradiative transitions were highly suppressed, blooming the phosphorescence of these ICZs at room temperature, the brilliant afterglow can be straight witnessed by the naked eyes. Impressively, the highest photoluminescence efficiency of 31.06% was obtained by the ICZ– o , the longest afterglow lasting time and phosphorescent lifetime of 35 s and 2.32 s were achieved by the ICZ– p 2, rivaling to the reported organic amorphous afterglows. It’s believed that the synthetic, crystal structural and afterglow studies of the ICZ families should find a promising avenue for developing new organic amorphous afterglow materials and their applications.