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Upon titration of MP-Zn with C12-2 at a concentration of
.25 mM, however, the fluorescence band centred at 545 nm
J. Am. Chem. Soc., 2013, 135, 5990; ( f ) Y. Tian, Y. Shi, Z. Yang and
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1
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showed a significant increase in its intensity (Fig. 3c). Of difference
was that only slight fluorescence enhancement was observed when
the solution of MP-Zn was treated with C12-1 (Fig. S16, ESI†).
(
4
c) A. V. Ambade, S. K. Yang and M. Weck, Angew. Chem., Int. Ed., 2009,
8, 2894; (d) F. Wang, J. Zhang, X. Ding, S. Dong, M. Liu, B. Zheng,
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According to the aggregation-enhanced emission, when the
S. Li, L. Wu, Y. Yu, H. W. Gibson and F. Huang, Angew. Chem., Int. Ed.,
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intra- and/or inter-molecular rotations of non-planar lumino-
genic molecules are restricted, the non-radiative pathway is
blocked and the radiative channel is opened, both of which
cause an enhanced emission. Due to the host–guest recognition
between DB24C8 and DBA groups, the intramolecular rotations
were partly restricted at the molecular level, which induced the
emission enhancement. These phenomena were in agreement
2012, 41, 5950; ( f ) L. He, S. Bi, H. Wang, B. Ma, W. Liu and W. Bu,
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X. Ding, Y. Yu and F. Huang, Adv. Mater., 2012, 24, 362; (h) G. Du,
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W. Weng and H. Xia, Macromolecules, 2013, 46, 8649; (k) X. Yan, S. Li,
J. B. Pollock, T. R. Cook, J. Chen, Y. Zhang, X. Ji, Y. Yu, F. Huang and
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X. Fang, Y. Lin, Y. Xu and W. Weng, ACS Macro Lett., 2014, 3, 141;
9b–f
with the reported organometallic luminogens.
As shown in
the DLS plots (Fig. S17, ESI†), upon addition of C12-1, the size
distribution of the resulting complex became broad. Compara-
(
n) J. Zhan, Q. Li, Q. Hu, Q. Wu, C. Li, H. Qiu, M. Zhang and S. Yin,
tively, the addition of C12-2 resulted in a sharp increase in the D
h
Chem. Commun., 2014, 50, 722; (o) X. Hu, T. Xiao, C. Lin, F. Huang and
L. Wang, Acc. Chem. Res., 2014, 47, 2041; ( p) E. Elacqua, D. S. Lye and
M. Weck, Acc. Chem. Res., 2014, 47, DOI: 10.1021/ar500128w.
from 158 to 5450 nm, indicating the presence of larger aggre-
gates in the resulting solution. The TEM image showed that an
interconnected film was formed (Fig. S18, ESI†). This cross-
linked network further restricted the intermolecular rotations
4
(a) T. Oku, Y. Furusho and T. Takata, Angew. Chem., Int. Ed., 2004, 43, 966;
(
b) W. Ong, J. Grindstaff, D. Sobransingh, R. Toba, J. M. Quintela,
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(
Fig. 3d) and thus the resulting fluorescence was significantly
(
4
d) E. R. Kay, D. A. Leigh and F. Zerbetto, Angew. Chem., Int. Ed., 2007,
6, 72; (e) J. J. Gassensmith, J. M. Baumes and B. D. Smith, Chem.
enhanced. At the intermediate concentrations of 12.5 and 125 mM,
no significant changes were detected in their fluorescence
intensities (Fig. S16, ESI†).
Commun., 2009, 6329; ( f ) Z. B. Niu and H. W. Gibson, Chem. Rev., 2009,
109, 6024; (g) L. Fang, M. A. Olson, D. Ben ´ı tez, E. Tkatchouk,
W. A. Goddard III and J. F. Stoddart, Chem. Soc. Rev., 2010, 39, 17.
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In summary, we have constructed a supramolecular polymer
5
6
MP-Zn bearing DB24C8 arms by coordinating Zn(OTf) with a
2
ditopic TPY-1 in situ. This metallosupramolecular polymer shows
concentration-dependent and acid–base controllable emissions.
Such dual responsiveness is highly important to develop a new
kind of fluorescence materials and molecular devices.
This work was supported by the NSFC (51173073), the Program for
New Century Excellent Talents in University (NCET-10-0462), the
1
30, 2073; (d) F. Schl u¨ tter, A. Wild, A. Winter, M. D. Hager, A. Baumgaertel,
C. Friebe and U. S. Schubert, Macromolecules, 2010, 43, 2759; (e) A. Wild,
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Fundamental Research Funds for the Central Universities (lzujbky- 7 (a) J. Kim, D. T. McQuade, S. K. McHugh and T. M. Swager, Angew.
Chem., Int. Ed., 2000, 39, 3868; (b) S. W. Thomas, G. D. Joly and
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014-74) and the Open Project of State Key Laboratory of Supra-
molecular Structure and Materials of Jilin University (sklssm201405).
8
9
T. L. Andrew and T. M. Swager, J. Polym. Sci., Part B: Polym. Phys.,
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0844 | Chem. Commun., 2014, 50, 10841--10844
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