Activating efficient phosphorescence from purely organic materials by crystal design

• Published in: Nature chemistry Vol. 3; no. 3; pp. 205 - 210
• Main Authors: Bolton, Onas, Lee, Kangwon, Kim, Hyong-Jun, Lin, Kevin Y., Kim, Jinsang
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.03.2011; Nature Publishing Group
• Subjects: 639/638/298; 639/638/403; 639/638/439; Aldehydes; Analytical Chemistry; Biochemistry; Bromine; Carbonyl compounds; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Crystallization; Crystals; Design; Engineering; Fluorescent Dyes - chemistry; Halogens - chemistry; Inorganic Chemistry; Molecular Conformation; Organic Chemicals - chemistry; Organic Chemistry; Organic compounds; Organometallic Compounds - chemistry; Phosphorus - chemistry; Physical Chemistry; Quantum Theory; Triplets; Ann Arbor Michigan; United States > US; Michigan
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/nchem.984

Phosphorescence is among the many functional features that, in practice, divide pure organic compounds from organometallics and inorganics. Considered to be practically non-phosphorescent, purely organic compounds (metal-free) are very rarely explored as emitters in phosphor applications, despite the emerging demand in this field. To defy this paradigm, we describe novel design principles to create purely organic materials demonstrating phosphorescence that can be turned on by incorporating halogen bonding into their crystals. By designing chromophores to contain triplet-producing aromatic aldehydes and triplet-promoting bromine, crystal-state halogen bonding can be made to direct the heavy atom effect to produce surprisingly efficient solid-state phosphorescence. When this chromophore is diluted into the crystal of a bi-halogenated, non-carbonyl analogue, ambient phosphorescent quantum yields reach 55%. Here, using this design, a series of pure organic phosphors are colour-tuned to emit blue, green, yellow and orange. From this initial discovery, a directed heavy atom design principle is demonstrated that will allow for the development of bright and practical purely organic phosphors. Purely organic materials are usually considered non-phosphorescent. Here, a crystal design that relies on the formation of halogen bonds is used to combine the heavy-atom effect with the triplet-state emission from aromatic carbonyls to produce organic crystals with bright phosphorescence of the type formerly observed only from inorganic and organometallic materials.