Luminescent sp2-Carbon-Linked 2D Conjugated Polymers with High Photostability

Abstract

Luminescent organic materials with high photostability are essential in optoelectronics, sensor, and photocatalysis applications. However, small organic molecules are generally sensitive to UV irradiation, giving rise to chemical decompositions. In this work, we demonstrate two novel CN-substituted two-dimensional sp2-carbon-linked conjugated polymers (2D CCPs) containing a chromophore triphenylene unit. The Knoevenagel polymerization between 2,3,6,7,10,11-hexakis(4-formylphenyl)triphenylene (HFPTP) and 1,4-phenylenediacetonitrile (PDAN) or 2,2′-(biphenyl-4,4′-diyl)diacetonitrile (BDAN), provides the crystalline 2D CCP-HFPTP-PDAN (2D CCP-1) and 2D CCP-HFPTP-BDAN (2D CCP-2) with dual pore structures, respectively. 2D CCP-1 and 2D CCP-2 exhibit the photoluminescence quantum yield (PLQY) up to 24.9 and 32.3%, which are the highest values among the reported 2D conjugated polymers and π-conjugated 2D covalent organic frameworks. Furthermore, compared with the well-known emissive small molecule tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), both 2D CCPs show superior photostability under UV irradiation for 2 h, profiting from the twisted and rigid structures of the CN-substituted vinylene linkages. The present work will trigger the further explorations of novel organic emitters embedded in 2D CCPs with high PLQY and photostability, which can be useful for optoelectronic devices.