Considering that heavy halogen atoms can be used to tune the emissive properties of organic luminogens, the understanding of their role in photophysics is fundamental for materials engineering. Here, the extrinsic and intrinsic heavy-atom effects on the photophysics of organic crystals were separately evaluated by comparing cyclic triimidazole (TT) with its monoiodo derivative (TTI) and its co-crystal with diiodotetrafluorobenzene (TTCo). Crystals of TT showed room-temperature ultralong phosphorescence (RTUP) originated from H-aggregation. TTI and TTCo displayed two additional long-lived components, the origin of which is elucidated through single-crystal X-ray and DFT/TDDFT studies. The results highlight the different effects of the I atom on the three phosphorescent emissions. Intrinsic heavy-atom effects play a major role on molecular phosphorescence, which is displayed at room temperature only for TTI. The H-aggregate RTUP and the I⋅⋅⋅N XB-induced (XB=halogen bond) phosphorescence on the other side depend only on packing features.

Intrinsic and Extrinsic Heavy-Atom Effects on the Multifaceted Emissive Behavior of Cyclic Triimidazole / E. Lucenti, A. Forni, C. Botta, C. Giannini, D. Malpicci, D. Marinotto, A. Previtali, S. Righetto, E. Cariati. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 25:10(2019 Feb 18), pp. 2452-2456. [10.1002/chem.201804980]

Intrinsic and Extrinsic Heavy-Atom Effects on the Multifaceted Emissive Behavior of Cyclic Triimidazole

E. Lucenti
Primo
;
A. Forni
;
C. Giannini;D. Marinotto;A. Previtali;S. Righetto;E. Cariati
2019-02-18

Abstract

Considering that heavy halogen atoms can be used to tune the emissive properties of organic luminogens, the understanding of their role in photophysics is fundamental for materials engineering. Here, the extrinsic and intrinsic heavy-atom effects on the photophysics of organic crystals were separately evaluated by comparing cyclic triimidazole (TT) with its monoiodo derivative (TTI) and its co-crystal with diiodotetrafluorobenzene (TTCo). Crystals of TT showed room-temperature ultralong phosphorescence (RTUP) originated from H-aggregation. TTI and TTCo displayed two additional long-lived components, the origin of which is elucidated through single-crystal X-ray and DFT/TDDFT studies. The results highlight the different effects of the I atom on the three phosphorescent emissions. Intrinsic heavy-atom effects play a major role on molecular phosphorescence, which is displayed at room temperature only for TTI. The H-aggregate RTUP and the I⋅⋅⋅N XB-induced (XB=halogen bond) phosphorescence on the other side depend only on packing features.
co-crystals; halogen bonding; phosphorescence; photophysics; time-resolved spectroscopy; Catalysis; Organic Chemistry
Settore CHIM/03 - Chimica Generale e Inorganica
Settore CHIM/06 - Chimica Organica
18-dic-2018
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/622887
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