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ChemComm
DOI: 10.1039/C3CC49208G
appearance of the same refraction peaks as those of the crystal in
the XRD patterns and the birefringence patterns upon polarizing
microscopy observation (Figs. S7 and S5). These results suggest
that the permeation of vapors of solvents in the ground film or
heating film increases the mobility of BVDP molecules, which
promotes the rearrangement of molecules from a metastable
School of Chemistry and Materials Science, Heilongjiang University
No. 74, Xuefu Road, Nangang District, Harbin, P. R. China
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†
Electronic Supplementary Information (ESI) available: [detailed
synthesis experiment, tiration absorption and emission spectra of BVDP
in solutions, NMR spectra of BVDP before and after adding trifluoro
acetic acid, absorption spectra, polarizing microscopy images and XRD
patterns of films, and the cif file for BVDP crystal]. See
DOI: 10.1039/b000000x/
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amorphous structure to a more stable crystalline Bꢀfrom state.
As previously described, BVDP exhibited PFC behavior, but
its fluorescence change, with a small spectral shift of 29 nm, was
not evident. Given the significant alteration in the fluorescence
spectrum after BVDP bound a proton to form the BVDP+H
complex, we expected that proton could modulate its PFC
properties. When the ground Gꢀform film was exposed to HCl
vapor, the yellowꢀgreen film immediately turned into a dark red
film (Rꢀform), which emitted weak red fluorescence with a
maximum at 639 nm (Fig. 2b) and had three absorption peaks at
1
S. Xu, H. Lu, X. Zheng, and L. Chen, J. Mater. Chem. C, 2013, 1,
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70
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. Z. Chi, X. Zhang, B. Xu, X. Zhou, C. Ma, Y. Zhang, S. Liu and J. Xu,
Chem. Soc. Rev., 2012, 41, 3878; X. Zhang, Z. Chi, Y. Zhang, S. Liu
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07, 534, and 595 nm (Fig. S4), suggesting that BVDP bound
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Li, L. Ye, B. Zou, W. Tian, Angew. Chem. Int, Ed., 2012, 51, 10782.
proton. No birefringence patterns can be observed, indicating a
disordered film. Interestingly, this red film can transfer into an
orange film (Oꢀform), emitting strong orange fluorescence with a
maximal emission peak at 564 nm, having three absorption peaks
at 445, 491, and 530 nm, and exhibiting birefringence patterns.
The result illustrates that the treatment of solvent promotes the
phase transition from a disordered to a crystal structure, linking
above the case without HCl vapor steaming. Moreover, the Oꢀ
form film can retransfer into the Rꢀform by mechanical shearing,
accompanied by a large emission spectral redshift of 75 nm. Such
transformation of fluorescence color is reversible by grindingꢀ
fuming circulation. Thus, a large contrast piezofluorochromism
can be realized by the protonation of BVDP. Notably, the Oꢀform
film can turn into Bꢀform by annealing at 70 °C for 10 min.
Moreover, the inverse transition from Bꢀform to Oꢀform was
achieved upon exposure of HCl vapor.
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In summary, a nonplanar triphenylamineꢀbased benzoxazole
derivative called BVDP was designed and synthesized. This
compound exhibited typical ICT characteristics and luminescence
mechanochromism. However, only lowꢀcontrast fluorescent color
change (a spectral shift of 29 nm) was observed. When BVDP
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bound a proton to form BVDP+H complex, a high contrast 105
piezofluorochromism with a large spectral change of 75 nm was
achieved. This finding suggests that additional external stimuli
can significantly affect and enhance the PFC properties of
materials.
This work was financially supported by the National Natural
Science Foundation of China (21103067, 21374041, and
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1102081), the Youth Science Foundation of Jilin Province
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Notes and references
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State Key Laboratory of Supramolecular Structure and Materials,
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College of Chemistry, Jilin University, Changchun, P. R. China, E-mail:
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State Key Laboratory of Theoretical and Computational Chemistry,
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Institute of Theoretical Chemistry, Jilin University, Changchun, P. R.
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Key Laboratory of Functional Inorganic Material Chemistry (MOE)
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