三苯胺取代的苯并咪唑的两种晶体:具有不同颜色的摩擦发光与相反发射位移的力致荧光变色

doi:10.6023/A19080306

摘要/Abstract

通过芳香亲核取代、还原以及DMSO/空气条件下的氧化成环反应合成了（4-二苯氨基苯基）-1H-苯并咪唑基苯腈（TBIM），化合物的溶液经挥发获得两种晶体TBIM_B与TBIM_G，前者具有深蓝色荧光（435 nm）而后者则具有绿色荧光（505 nm）.受力后两者均成为具有青色荧光（457 nm）的无定形粉末，在溶剂熏蒸或热退火条件下前者的荧光可完全恢复，而后者只能转变为前者的荧光.此外，TBIM_B与TBIM_G晶体受力后可分别发出蓝色（432 nm）和绿色（500 nm）的闪光.两种晶体都属于中心对称空间群且晶体内分子对的净偶极矩几乎为零，压电效应与破碎晶体表面分子对间的放电激发理论并不适用于解释两种晶体的摩擦发光.分子的链状堆积结构使晶体在受力下很容易发生解理并引起解理面之间的相对运动导致内生摩擦放电，从而激发解理面上的分子使之产生荧光辐射，这种机制很有可能是该两种晶体出现摩擦发光活性的主要原因.

关键词: 力致荧光变色, 摩擦发光, 多晶体, 内生摩擦放电, 苯并咪唑

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

引用此文

刘笑静, 贾彦荣, 江豪, 高贯雷, 夏敏. 三苯胺取代的苯并咪唑的两种晶体:具有不同颜色的摩擦发光与相反发射位移的力致荧光变色[J]. 化学学报, 2019, 77(11): 1194-1202.

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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图/表 12

图式1. 化合物TBIM的合成路线

Schema 1. Synthetic route to compound TBIM

图 1. TBIM在不同极性溶剂中的吸收光谱(实线)与发射光谱(虚线) (插图: 365 nm紫外光照下溶液的荧光照片: 1—正己烷; 2—苯; 3—二氯甲烷; 4—丙酮; 5—乙腈)

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)

图 2. (A) TBIMB与TBIMG晶体中分子的构象以及(B)两者中的分子在该构象下的HOMO-LUMO能级与能差

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

图 3. TBIMG (A)与TBIMB (B)晶体中分子的堆积(为了清楚起见TBIMB晶体中的溶剂分子已抽取)

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

图 4. TBIMG (A)与TBIMB (B)晶体中以及两者无定形状态下(C)分子激发态构象示意图

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

图 5. TBIMG晶体的二向色性照片

Figure 5. Photos of TBIMG crystal for its dichorism

图 6. TBIMG (A)和TBIMB (B)在不同固体状态下的发射光谱

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

图 7. TBIMB (A, C)和TBIMG (B, D)在不同固体状态下的PXRD图形

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

图 8. TBIMG和TBIMB在不同固体条件下转化的能量示意图

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

图 9. TBIMG (A)和TBIMB (B)晶体的摩擦发光光谱、研磨前后的光致发射光谱(插图:黑暗处两种晶体摩擦发光的照片)

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

图 10. 晶体TBIMG和TBIMB中分子对的前线轨道能级、能级差以及偶极矩

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

图 11. TBIMG (A)和TBIMB (B)晶体中的链状分子堆积

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

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