DOI: 10.1039/C6CC03248F
ChemComm
‡
Footnotes should appear here. These might include comments relevant
emitting the distinct bright green fluorescence only in the
scratched areas in contrast to the blue surrounding regions. We
noticed that the characters disappeared respectively in 5 minutes
at room temperature and in 2 minutes at 40 ℃. The relative
intensity ratio of the shoulder band at 432 nm to that at 490 nm
increased gradually with time at room temperature. The ratio was
measured to 0.66 for a freshly sheared sample, but it increased to
to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
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6
7
0
5
0
(a) S. J. K. Toal, A. Jones, D. Magde, W. C. Trogler, J. Am.Chem.
Soc., 2005, 127, 11661; (b) M. Irie, T. Fukaminato, T. Sasaki, N.
Tamai, T. Kawai, Nature, 2002, 420, 759; (c) D. Pauluth, K. Tarumi,
J. Mater. Chem., 2004, 14, 1219; (d) M. K. Beyer, H. Clausen-
Schaumann, Chem. Rev., 2005, 105, 2921; (e) A. L. Balch, Angew.
Chem. Int. Ed., 2009, 48, 2641; (f) Y. Zhao, H. Gao, Y. Fan, T. Zhou,
Z. Su, Y. Liu, Y. Wang, Adv. Mater., 2009, 21, 3165; (g) L. Wang,
Y. Zhou, J. Yan, J. Wang, J. Pei, Y. Cao, Langmuir, 2009, 25, 1306.
(a) X. M. Sun, J. Zhang, X. Lu, X. Fang and H. S. Peng, Angew.
Chem. Int. Ed., 2015, 54, 3630; (b) M. S. Yuan, D. E. Wang, P. C.
Xue, W. J. Wang, J. C. Wang, Q. Tu, Z. Q. Liu, Y. Liu, Y. R. Zhang
and J. Y. Wang, Chem. Mater., 2014, 26, 2467; (c) M. A. Squillaci, L.
Ferlauto, Y. Zagranyarski, S. Milita, K. Müllen and P. Samorì, Adv.
Mater., 2015, 27, 3170.
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0
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0
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.13 after 5 minutes. The increase of the ratios reflects the
metastable state of PPB formed by shearing can spontaneously
transform back to the stable state with high energy emission
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(shorter wavelength emission). As shown in Fig. 5f, the cycle of
writing and spontaneous erasing process can be repeated many
times. Therefore, this ML material can be used to make a writing
board or paper with a spontaneous erasing function. Since the
erasing process is spontaneous without any external stimulation,
such as organic solvents, heating, or light, this material shows
remarkable advantages such as environmental friendly and cost-
effect.
75
80
(a) X. F. Wang, J. L. Wang, Y. Si, B. Ding, J. Y. Yu, G. Sun, W.J.
Luo and G. Zheng, Nanoscale, 2012, 4, 7585; (b) Y. F. Zhao, H. Z.
Gao, Y. Fan, T. L. Zhou, Z. M. Su, Y. Liu, Y. Wang, Adv. Mater.,
2
2
009, 21, 3165; (c) I. Duboriz, A. Pud, Sensors and Actuators B,
014, 190, 398; (d) N. S. S. Kumar, S. Varghese, N. P. Rath, S. Das,
In summary, the two pyrene boronic acid cyclic esters, PPB
and NPB, were synthesized and their fluorescent properties in
solid and solution were investigated. It was found that the PPB
solid exhibited fast self-recovering ML property with color
changed from blue to green at room temperature, whereas NPB
did not, although they had similar chemical structures. The results
of nanoindentation measurement and single crystal X-ray
diffraction demonstrated that the mechanical responsive
fluorescent properties of PPB and NPB were highly related to the
molecular packing in the solid states, and the much softer and
more compliant PPB crystal could facilitate the formation of
recoverable and low energy defects in the structure because the
presence of slip planes. To the best of our knowledge, PPB is the
first example of ML material based on boronic acid ester. Since
the mechanoluminescence process of this material is quickly
reversible, it can be used to make dynamic data storage or writing
board with self-erasing function without using any organic
solvents, heating, or light. Therefore, in comparison of other ML
materials, there are remarkable advantages, such as environment-
friendly, energy-saving and cost-effective. In addition, this
research provides a strategy for design and preparation of self-
recovering mechanical responsive fluorescent materials. Further
study is underway.
J. Phys. Chem. C, 2008, 112, 8429; (e) T. Mutai, H. Satou, K. Araki,
Nat. Mater., 2005, 4, 685; (f) R. Davis, N. P. Rath, S. Das, Chem.
Commun., 2004, 74; (g) M. J. Teng, G. C. Kuang, X. R. Jia, M. G. Y.
Li, Y. Wei, J. Mater. Chem., 2009, 19, 5648.
(a) W. Li, L. Wang, J. P. Zhang and H. Wang, J. Mater. Chem. C,
2014, 2, 1887;(b) Z. Y. Ma, M. J. Teng, Z. J. Wang, S. Yang and X.
R. Jia, Angew. Chem. Int. Ed., 2013, 52, 12268; (c) M. J. Teng, X. R.
Jia, S. Yang, X. F. Chen and Y. Wei, Adv. Mater., 2012, 24, 1255;
4
8
9
9
5
0
5
(d) Y. Sagara, T. Mutai, I. Yoshikawa and K. Araki, J. Am. Chem.
Soc., 2007, 129, 1520; (e) H. J. Kim, D. R. Whang, J. Gierschner, C.
H. Lee and S. Y. Park, Angew. Chem. Int. Ed., 2015, 54, 4330; (f) R.
H. Pawle, T. E. Haas, P. M¨ullerb and S. W. Thomas, Chem. Sci.,
2014, 5, 4184; (g) G. Q. Zhang, J. W. Lu and C. L. Fraser, Inorganic
Chemistry, 2010, 49, 23; (h) N. Mizoshita, T. Tani and S. Inagaki,
Adv. Mater., 2012, 24, 3350; (i) Z. G. Chi, X. Q. Zhang, B. J. Xu, X.
Zhou, C. Q. Ma, Y. Zhang, S. W. Liua and J. R. Xu, Chem. Soc. Rev.,
2
012, 41, 3878.
5
6
7
(a) G. Q. Zhang, J. W. Lu, M. Sabat and C. L. Fraser, J. Am. Chem.
Soc., 2010, 132, 2160; (b) T. Butler, W. A. Morris, J. S. Kosicka, and
C. L. Fraser, ACS Appl. Mater. Interfaces, 2016, 8, 1242.
A. S. Batsanov, J. A. K. Howard, D. A. ꢀoꢁꢂꢃ J. C. Collings, Z. Q.
Liu, I. A. I. Mkhalid, M. H. Thibault, and T. B. Marder, Cryst.
Growth Des., 2012, 12, 2794.
1
1
1
1
1
1
00
05
10
(a) L. Liu, D. Zhang, G. Zhang, J. Xiang, D. Zhu, Org. Lett., 2008,
1
0, 2271; (b) J. K. Choi, S. H. Kim, J. Yoon, H. K. Lee, R. A.
Bartsch, J. S. Kim, J. Org. Chem., 2006, 71, 8011; (c) M. Hariharan,
S. C. Karunakaran, D. Ramaiah, Org. Lett., 2007, 9, 417; (d) A. F. M.
Kilbinger, R. H. Grubbs, Angew. Chem. Int. Ed., 2002, 41, 1563; (e)
E. H. W. Pap, A. Hanicak, A. van Hoek, K .W. A. Wirtz, A. J. W. G.
Visser, Biochemistry, 1995, 34, 9118.
We thank National Natural Science Foundation of China (No.
8
9
K. Kalyanasundaram and J. K. Thomas, J. Am. Chem. Soc., 1977, 99,
2
1474093) for financial support.
2
039.
(a) Y. Tsujii, T. Itoh, T. Fukuda and T. Miyamoto, Langmuir, 1992,
4
5
Notes and references
8
, 936; (b) N. Tamai, J. Yonezawa, Y. Nishimura, I. Yamazaki and I.
a
Yamazaki, J. Phys. Chem., 1992, 96, 1967.
CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer
15 10 F. M. Winnik, Chem. Rev., 1993, 93, 587.
Th. Förster, Angew. Chem. Int. Ed., 1969, 8, 333.
Science and Engineering, University of Science and Technology of China,
Hefei 230026, P. R. China. E-mail: bairk@ustc.edu.cn.
1
1
b
12 (a) M. S. R. N. Kiran, S. Varughese, U. Ramamurty, G. R. Desiraju,
CrystEngComm, 2012, 14, 2489; (b) M. S. R. N. Kiran, S.
Varughese, C. M. Reddy, U. Ramamurty, G. R. Desiraju, Cryst.
Growth Des., 2010, 10, 4650; (c) K. J. Ramos, D. E. Hooks, D. F.
Bahr, Philos. Mag., 2009, 89, 2381; (d) J. C. Tan, A. K. Cheetham,
Chem. Soc. Rev., 2011, 40, 1059.
Department of Chemistry, University of Massachusetts-Amherst, 300
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Massachusetts Ave, Amherst, Massachusetts 01003, United States. E-mail:
wbai@chem.umass.edu.
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†
Electronic Supplementary Information (ESI) available: Detailed
experimental procedures for all optical, x-ray diffraction, and differential
scanning calorimetry (DSC) experiments are reported in the Supporting
Information. Crystallographic data for the structural analysis of PPB and
NPB have been deposited with the Cambridge Crystallographic Data
Center (CCDC 911404, CCDC 911403). See DOI: 10.1039/b000000x/
1
3 C. M. Reddy, R. C. Gundakaram, S. Basavoju, M. T. Kirchner, K. A.
Padmanabhan, G. R. Desiraju, Chem. Commun., 2005, 3945; (b) C.
M. Reddy, M. T. Kirchner, R. C. Gundakaram, K. A. Padmanabhan,
G. R. Desiraju, Chem. Eur. J., 2006, 12, 2222.
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