Two dithiophene aldehyde/ketone derivatives are designed as luminescence molecular rotors, i.e., 1,1'-([2,2'-bithiophene]-3,3'-diyl)bis(ethan-1-one) (BTBE) and 3'-acetyl-[2,2'-bithiophene]-3-carbaldehyde (BTAC). Their absorption and luminescence properties, as well as the stimulus responsive luminescence characteristics of water spikes are studied in detail. In order to further explore relationship of luminescence and molecular structure, three reference compounds are also synthesized, named 1-(2-methylthiophen-3-yl)ethanone (MTE), 2-methylthiophene-3-carbaldehyde (MTC) and 4H-cyclohepta[1,2-b:7,6-b']dithiophen-4-one (CDTO). BTBE and BTAC have two obvious absorption bands in the short wavelength region with peak wavelengths of about 212 nm and 260 nm, respectively, while there is a weak trailing type absorption band in the range of about 300-400 nm. Their fluorescence spectra show two luminescence bands in the range of 280-350 nm and 400-600 nm, respectively, and the latter is stronger. Compared with the absorption and luminescence spectra of the reference compounds, it is determined that two absorption bands of BTBE and BTAC in shorter wavelength region are derived from the single thiophene ring carbonyl planar unit, while the absorption band in longer region are derived from the integrated structure of dithiophene carbonyl. The fluorescence bands with peaks of about 300 nm and 470 nm originate respectively from the localized F-C vertical excited states (LE), i.e., the excited state from single planar thienyl-carbonyl unit, and integrated excited state (IE), i.e., the excited state from integrated di-thienyl-carbonyl rings linked covalently with less dihedral angle and greater degree of conjugation at excited state. The crystal structure data show that two thiophene rings possess larger dihedral angles in crystal states, 86.9° for BTBE and 60.8° for BTAC, respectively. However, theoretical calculation results prove the conformational stabilization energy changes little, less than 1.5 kcal/mol, as dihedral angle changes from 50° to 100°. Hydrogen bonding is sufficient to overcome the energy required for this conformational change. Therefore, both BTBE and BTAC can produce water stimulation response luminescence behavior. This stimulating response behavior of BTBE and BTAC can be applied to the preparation of water writable film materials.
Keywords: Dithiophene aldehyde/ketone derivatives; Fluorescence; Hydrogen bonding; Molecular rotors; Stimulus responsive luminescence; Water writable film materials.
Copyright © 2022 Elsevier B.V. All rights reserved.