Anthracene–naphthylacetonitrile fluorescent isomers and Cl/H substituent dependent molecular packing, solid-state fluorescence and mechanofluorochromism

Abstract

The condensation reaction between naphthylacetonitrile isomers and anthracene aldehyde produced unexpected highly twisted AIEgens (2-(naphthalen-1-yl)-2-(10-oxo-9,10-dihydroanthracen-9-yl)acetonitrile (1) and (Z)-3-(anthracen-9-yl)-2-(naphthalen-2-yl)acrylonitrile (2)). 1 and 2 exhibited strong solid-state fluorescence and mechanical stimuli-induced reversible fluorescence switching. Crystallization of 2 in acidic CHCl₃–CH₃OH produced Cl substituted anthracene (2-Cl), whereas in CH₂Cl₂ pure crystals of 2 were produced. Single crystal analysis of 1 revealed a twisted conformation in the middle ring of anthracene due to carbonyl introduction. The carbonyl oxygen and cyano nitrogen are involved in the H-bonding interactions in the crystal lattice. 2 showed slipped stacking between naphthyl units whereas 2-Cl exhibited intermolecular H-bonding between Cl and anthracene hydrogens. 1 exhibited strong solid-state fluorescence (λ_max = 541 nm, quantum yield (Φ_f) = 18.2%), whereas 2 and 2-Cl displayed tunable and relatively low fluorescence efficiency (λ_max = 547 (2), 489 nm (2-Cl), Φ_f = 6.3 (2) and 3.6% (2-Cl)). Computational studies suggested clear intramolecular charge transfer (ICT) in 1 compared to 2 and 2-Cl. Further, 1 and 2-Cl showed mechanical crushing and heating induced reversible fluorescence switching but 2 did not show any fluorescence switching. Powder X-ray diffraction indicated a reversible phase transformation upon crushing and heating that caused reversible fluorescence switching. Hence, the present study provides insight into the subtle structural impact on intermolecular interactions and solid-state fluorescence.