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Modulating Room-Temperature Phosphorescence through the Synergistic Effect of Heavy-Atom Effect and Halogen Bonding

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posted on 16.07.2021, 15:04 by Liming Lai, Bing Fang, Mingyu Fan, Wenyu Cheng, Meizhen Yin
Organic room-temperature phosphorescence (RTP) materials have been paid great attention for their promising applications in anticounterfeiting, optical device, and bioimaging. However, owing to inefficient intersystem crossing (ISC), it still remains a challenge to develop organic RTP materials with both high quantum yields (Φp) and long lifetime (τp). Herein, a reasonable strategy is presented to modulate and balance the Φp and τp through the synergy effect of halogen bonding and heavy-atom effect (HAE). Modulated RTP properties are successfully achieved by the introduction of halogen atoms into 4-(9-H-carbazol-9-yl) benzonitrile due to enhanced ISC. Especially, CzBzBr shows the highest Φp of 23.50% and CzBzCl exhibits the longest τp of 607.4 ms. The excessive HAE of the bromine atom decreases the τp of CzBzBr, while moderate HAE of the chlorine atom endows CzBzCl with both high Φp and long τp. In addition, the halogen bondings lead to specific halogen-mediated molecular cluster packing, further suppressing nonradiative transition for ultralong RTP emission. Through simple physical co-crystallization with adjusting the mass ratio of CzBzCl/CzBzBr, co-crystals with modulated RTP properties and white-light emission phenomena are obtained. Our study provides a rationale method to develop modulated high-efficiency RTP materials, which will expand their practical applications.