New Journal of Chemistry
Page 6 of 7
can be obtained free of charge from The Cambridge Crystallographic
enhanced fluorescence could be correlated to the variations in the
molecular packing.29 This indicates that the solid state
photochromism is not due to transꢀ to cisꢀ transformation. We
tried to photoirradiate the crystal of 1 with different wavelength,
but the crystal structure of 1 does not change upon UV irradiation,
even with 500nm or 750nm of 4W laser irradiation. The fact that
the XRD patterns of 1 before and after UV irrradiation are more
or less the same (Fig.11) further proves that the solid state
10 photocoloration of 1 does not result from the change in the crystal
structure. The transꢀ to cisꢀcrystal transformation of 1 is difficult
to take place in the crystalline phase. The photocoloration of the
solid state may probably be ascribed to the changes in the
geometry of the molecule and the molecular packing.
‡1 Xꢀray Structure for Eꢀ1: transꢀC13H12N4O, M = 240.27 , orthorhombic
60 space group P212121, a = 5.187(3) Ǻ, b = 9.245(5) Ǻ, c = 25.359(1) Ǻ, α =
90°, β = 90°, γ = 90°, V = 1216.2(1) Ǻ3, Z = 4, ρcald = 1.31 gcmꢀ3, ꢂ =
0.088 mmꢀ1, F(000) = 504, T = 153(2)K, 5181 reflections measured, 1419
unique (Rint = 0.049), 809 (I > 2σ(I)) which were used in all calculations
with final R=0.034.(CCDC 739528)
65 ‡2 Xꢀray Structure csrystalized in acetone for Eꢀform: transꢀ2
(C13H12N4O)ꢁC3H6O, M = 523.59, orthorhombic space group Pbcn, a =
17.669(3) Ǻ, b = 8.668(1) Ǻ, c = 18.288(2) Ǻ, α = 90°, β = 109.72°, γ =
90°, V = 2835.9(1) Ǻ3, Z = 4, ρcald = 1.26 gcmꢀ3, ꢂ = 0.086 mmꢀ1, F(000) =
1135.7, T = 153(2)K, 12064 reflections measured, 2597 unique (Rint
70 0.038), 3375 (I > 2σ(I)) which were used in all calculations with final
R=0.076. (CCDC 824334)
‡3 Xꢀray Structure for Zꢀ1: cisꢀC13H12N4O, M = 240.27 , monoclinc space
group P1 21/C1, a = 22.602(7) Ǻ, b = 5.69(2) Ǻ, c = 20.209(7) Ǻ, α =
90°, β = 109.72°, γ = 90°, V = 2394.5(6) Ǻ3, Z = 8, ρcald = 1.33 gcmꢀ3, ꢂ =
75 0.089 mmꢀ1, F(000) = 1007.7, T = 153(2)K, 12309 reflections measured,
4676 unique (Rint = 0.039), 3375 (I > 2σ(I)) which were used in all
calculations with final R=0.071. (CCDC 758818)
5
=
15 Conclusions
E/Zꢀphotoisomerization of pyridine substituted semicarbazide
Schiff bases in solution was directly evidenced by the C=N
double bond photoisomerization. (E)ꢀ4ꢀPhenylꢀ1ꢀ(pyridineꢀ2ꢀ
ylmethylene)semicarbazide (1) exhibits photochromism in both
20 solution phase and the solid state. The photochromism of 1 in
solution was revealed to operate under the mechanism of C=N
transꢀcis photoisomerization. The solid state photochromism of 1
was shown to result from changes in the geometry of the
molecule and the molecular packing. The results are useful for
25 the design and synthesis of other similar Schiff bases showing
1
2
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We are grateful to the financial support of the Natural Science
Foundation of Fujian Province (grant no. 2010J01048), the
45 National Natural Science Foundation of China (grants nos.
21021061and 20973136) and NFFTBS (grant no. J1030415).
Finally, we thank professor Yunꢀbao Jiang for English improving.
115
Notes and references
Department of Chemistry, College of Chemistry and Chemical
50 Engineering, Xiamen University, Xiamen 361005, China. Eꢀmail:
linlr@xmu.edu.cn; Fax: +86 592 2183047; Tel: +86 0592ꢀ2185191
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† Supplementary data associated with this article can be found in the
online version, at DOI: 10.1039/b000000x/
55 CCDCꢀ758818 (Zꢀ1), and CCDCꢀ824334 (Eꢀ1 crystalized in acetone)
.
CCDCꢀ739528 (Eꢀ1),
125 25 L. R. Lin, W. X. Hu, J. Ma, H. Zhang, R.B. Huang and L. S. Zheng,
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