Two Polymorphs of Triphenylamine-substituted Benzo[d]imidazole: Mechanoluminescence with Different Colors and Mechanofluorochromism with Emission Shifts in Opposite Direction

doi:10.6023/A19080306

Abstract

Mechanofluorochromism (MFC) and mechanoluminescence (ML) are two types of significant solid-state optical phenomena which are closely dependent on conformations, packing modes and intermolecular interactions. Herein, through a three-step route involving aromatic nucleophilic substitution, reduction and oxidative cyclization in DMSO under air, a benzo[d]imidazole with triphenylamine and 4-cyanophenyl respectively located at C(2)- and N(1)-position is obtained in good yields. Two polymorphs TBIM_B and TBIM_G of 4-(2-(4-(diphenylamino)phenyl)-1H-benzo[d]imidazol-1-yl)benzonitrile (TBIM) corespondingly exhibit intense deep-blue (435 nm) and green fluorescence (505 nm). Under force stimuli, both polymorphs turn into amorphous phase with cyan fluorescence (457 nm). By fuming in solvent vapor or annealing treatment, only the ground TBIM_B sample can be completely restored into the original crystalline structure, the ground TBIM_G sample is just transformed into TBIM_Bcrystal. It is assumed that the enhanced energy barrier induced by the denser packing in TBIM_G crystal makes the conversion from in amorphous phase to crystalline one kinetically infeasible. The crystallography reveals that triphenylamine moiety in TBIM_G crystal is less restrained by intermolecular interactions than that in TBIM_B crystal, which results in the long-wavelength TICT emission in the former crystal and the short-wavelength LE emission in the latter one. In exposure to force stimuli, TBIM_B and TBIM_G crystals respectively give out the blue (432 nm) and green (500 nm) flash. It is revealed by crystallography that both polymorphs hold centrosymmetric space groups. DFT calculations based on the molecular couples with strong intermolecular interactions demonstrate that the close-to-zero net dipole moments occurs on these couples. Hence, neither piezoelectric effect nor excitation of molecules on cracked surfaces by discharges between molecular couples should account for the ML behaviors of these two polymorphs. Due to the readily force-induced cleavage of the two crystals by particular chain-shaped packing, the endogenous friction discharge caused by relative movements between cleavage planes would excite molecules on these planes, and this mechanism is assumed to be mainly responsible for the ML activity of the two crystals.

Key words: mechanofluorochromism, mechanoluminescence, polymorphs, endogenous friction discharge, benzimidazole

Cite this article

Liu Xiaojing, Jia Yanrong, Jiang Hao, Gao Guanlei, Xia Min. Two Polymorphs of Triphenylamine-substituted Benzo[d]imidazole: Mechanoluminescence with Different Colors and Mechanofluorochromism with Emission Shifts in Opposite Direction[J]. Acta Chimica Sinica, 2019, 77(11): 1194-1202.

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Fig. & Tab. 12

Schema 1. Synthetic route to compound TBIM

Figure 1. Absorption (solid lines) and emission spectra (dash lines) of TBIM in different solvents (Inserted: photos of solutions under 365 nm UV irradiation: 1—n-hexane; 2—benzene; 3—dichloromethane; 4—acetone; 5—acetonitrile)

Figure 2. (A) Molecular conformations in TBIMB and TBIMG crystals; (B) HOMO-LUMO levels and energy gaps of the double molecules under such conformations

Figure 3. Molecular packings in TBIMG (A) and TBIMB (B) crystals (solvent molecules in TBIMB crystal are squeezed in order to present clear view)

Figure 4. Schematic diagram of excited-state geometry for molecules in TBIMG (A) and TBIMB (B) crystals and in their amorphous phase (C)

Figure 5. Photos of TBIMG crystal for its dichorism

Figure 6. Solid-state emission spectra of TBIMG (A) and TBIMB (B) under different conditions

Figure 7. PXRD patterns of TBIMB (A, C) and TBIMG (B, D) under different solid-state conditions

Figure 8. Schematic diagram of potential energy during transformations of TBIMG and TBIMB under different solid-state conditions

Figure 9. ML and PL spectra of TBIMG (A)和TBIMB (B) (Inserted: ML photos of the two polymorphs)

Figure 10. HOMO-LUMO levels, energy gaps and dipole moments of molecular couples in TBIMG and TBIMB crystals

Figure 12. Chain-shaped packing in TBIMG (A) and TBIMB (B) crystals

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