Dynamic characterization of crystalline fluorophores with conformationally flexible tetrahydrocarbazole frameworks

• Published in: CrystEngComm Vol. 22; no. 22; pp. 3789 - 3796
• Main Authors: Colin-Molina, Abraham, Velázquez-Chávez, Diego, Jellen, Marcus J, Rodríguez-Cortés, Lizbeth A, Cifuentes-Quintal, Miguel Eduardo, Merino, Gabriel, Rodríguez-Molina, Braulio
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 14.06.2020
• Subjects: Aliphatic compounds; Chemical compounds; Chemical reactions; Coupling (molecular); Crystal structure; Crystallinity; Crystallography; Deuteration; Fluorescence; Format; NMR; Nuclear magnetic resonance; Solid state
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/d0ce00423e

Two new compounds 2 and 3 and their deuterated analogues ( 2 - d 4 and 3 - d 4 ) were prepared from Ullmann-type coupling reactions. Both molecules show good emissive properties in solution Φ F = 0.13 ( 2 ) and 0.57 ( 3 ) as well as in the solid-state ( Φ F = 0.35 and 0.33, respectively). Variable temperature solid-state NMR measurements using 13 C CPMAS and 2 H spin-echo helped to identify segmental motion in the phenylene as well as in the aliphatic moieties, which agreed well with the crystallographic disorder in these moieties. The rotational energy barriers for the new compounds were computed with a periodic DFT approach, finding asymmetric rotational potentials with barriers of 3.5 kcal mol −1 ( 2 ) and 4.5 kcal mol −1 ( 3 ) for 60° jumps and much higher barriers (>25 kcal mol −1 ) for 180° jumps. Our studies indicate that low frequency 4-fold motions coexist with fluorescence in these crystalline conjugated compounds. Fluorescent compounds 2 and 3 have been prepared by using Ullmann-type coupling reactions. Solid-state NMR ( 13 C CPMAS and 2 H) and periodic DFT computations were used to determine that intramolecular motion coexists with emission in these crystals.