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

文献信息

发布日期 2023-10-16

DOI 10.1039/D3CE00718A

影响因子 3.545

作者

Sasikala Ravi, Prakash Priyadharshini, Subramanian Karthikeyan, Vedichi Madhu, Dohyun Moon, Savarimuthu Philip Anthony

摘要

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 (λmax = 541 nm, quantum yield (Φf) = 18.2%), whereas 2 and 2-Cl displayed tunable and relatively low fluorescence efficiency (λmax = 547 (2), 489 nm (2-Cl), Φf = 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.

期刊推荐

Journal of the American Chemical Society

Analyst

Carbon

Corrosion Science

Advances in Colloid and Interface Science

Cement and Concrete Research

Biopolymers

Australian Journal of Chemistry

Bulletin of the Chemical Society of Japan

Doklady Chemistry

来源期刊

CrystEngComm

CiteScore: 5.5

自引率: 7.7%

年发文量: 643

CrystEngComm is the forum for the design and understanding of crystalline materials. We welcome studies on the investigation of molecular behaviour within crystals, control of nucleation and crystal growth, engineering of crystal structures, and construction of crystalline materials with tuneable properties and functions. We publish hypothesis-driven research into… how crystal design affects thermodynamics, phase transitional behaviours, polymorphism, morphology control, solid state reactivity (crystal-crystal solution-crystal, and gas-crystal reactions), optoelectronics, ferroelectric materials, non-linear optics, molecular and bulk magnetism, conductivity and quantum computing, catalysis, absorption and desorption, and mechanical properties. Using Techniques and methods including… Single crystal and powder X-ray, electron, and neutron diffraction, solid-state spectroscopy, spectrometry, and microscopy, modelling and data mining, and empirical, semi-empirical and ab-initio theoretical evaluations. On crystalline and solid-state materials. We particularly welcome work on MOFs, coordination polymers, nanocrystals, host-guest and multi-component molecular materials. We also accept work on peptides and liquid crystals. All papers should involve the use or development of a design or optimisation strategy. Routine structural reports or crystal morphology descriptions, even when combined with an analysis of properties or potential applications, are generally considered to be outside the scope of the journal and are unlikely to be accepted.