Research on Emission Behavior and Mechanofluorochromic Activity of Benzo[d]imidazoles with Region-isomerized Push-Pull Groups

doi:10.6023/A23070349

Abstract

Through the oxidation-cyclization of N-(4-cyanophenyl)-o-phenylenediamine and 1-pyrenylaldehyde or N-(1- pyrenyl)-o-phenylenediamine and 4-cyanobenzaldehyde in dimethyl sulfoxide under air, the two isomers BIM_NPy and BIM_CPywith pyrenyl and 4-cyanophenyl interchanged at N₁ and C₂ position on benzo[d]imidazole core were prepared while the photophysical properties of the double isomers in both solution and solid state were investigated. In solution, the emission of BIM_CPy exhibited a moderate solvatochromic effect but the emission of BIM_NPy was inert to the change of solvent polarity. The crystals of the two isomers displayed the blue-shifted mechanofluorochromic (MFC) behavior in response to force stimuli, but BIM_NPy crystals possess the larger MFC activity. Moreover, the MFC on BIM_NPy was reversible by fuming in solvent vapor or annealing and could be partly self-recovered at room temperature thanks to the less dense intermolecular interactions. However, the MFC on BIM_CPy was irreversible under annealing and could only be recovered by fuming due to the indispensability of solvent molecules to form crystal lattices. In aid of differential scanning calorimetry, powder and single crystal X-ray diffraction, emission decay spectra as well as theoretical calculations, the reasons for the different emission behavior of the two isomers in solution and solid state were explored. It was revealed that the S₂ excited state with both intramolecular charge transfer (ICT) and local emission (LE) features may account for the sensitive solvatochromism of BIM_CPy, while the S₂ excited state with only LE emission feature may be responsible for the inert solvatochromism of BIM_NPy. Moreover, the different solid-state emission performance and MFC activity should be attributed to the particular molecular packing in crystals of the two isomers. Fundamentally, the varied dipole moments and the distinguishing π-conjugation extents induced by the region-isomerization of pyrenyl and 4-cyanophenyl with the push-pull electronic capability could be considered as the primary cause for the remarkably macroscopic differences of physical properties on the two isomers.

Key words: mechanofluorochromism, region-isomerization, benzo[d]imidazole, pyrenyl, molecular packing

Cite this article

Yanrong Jia, Kai Xu, Yanying Zhao, Huagang Ni, Ying Wu, Min Xia. Research on Emission Behavior and Mechanofluorochromic Activity of Benzo[d]imidazoles with Region-isomerized Push-Pull Groups[J]. Acta Chimica Sinica, 2023, 81(12): 1716-1723.

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Fig. & Tab. 10

Figure 1. Representative structures of MFC-active systems with region- or position-isomerized groups (FS: force stimuli)

Figure 2. Synthetic routes of BIMNPy and BIMCPy

Figure 3. Absorption (dash lines on left) and emission spectra (λex=340 nm, solid lines on right) of BIMNPy (a) and BIMCPy (b) in different solvents (inserted: photos of solution under 365 nm UV light. 1: n-hexane; 2: benzene; 3: ethyl acetate; 4: dichloromethane; 5: acetonitrile)

Figure 4. Orbit energy levels and emission transition characteristics of BIMNPy (a) and BIMCPy (b) in gas phase and in acetonitrile solution (f: transition oscillator strength; ΔE: energy gap between orbits)

Figure 5. Dihedral angles of BIMNPy and BIMCPy in free (green) and crystalline state (orange), and molecular dipole moments in crystalline state

Figure 6. Molecular packings and intermolecular interactions in (a), (b) BIMNPy crystal and (c)~(e) BIMCPy crystal

Figure 7. Solid-state emission spectra and photos by 365 nm UV light of BIMNPy (a) and BIMCPy (b) under different conditions

Figure 8. Emission decay spectra of BIMNPy (a) and BIMCPy (b) under different conditions

Figure 9. PXRD patterns of BIMNPy (a) and BIMCPy (b) under different conditions

Figure 10. DSC of BIMNPy (a) and BIMCPy (b) under different solid- state conditions

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