DOI: 10.1002/chem.200903265
Molecular Logic Gates and Switches Based on 1,3,4-Oxadiazoles
Triggered by Metal Ions
Ai-Fang Li, Yi-Bin Ruan, Qian-Qian Jiang, Wen-Bin He, and Yun-Bao Jiang*[a]
Abstract: Organic molecular devices and Cl; 1a e) that form a bidentate es were dependent on the substi-
for information processing applications chelating environment for metal ions. tuent X, with those of 1d being the
are highly useful building blocks for These compounds showed fluorescence most substantial. The 1,3,4-oxadiazole
constructing molecular-level machines. response profiles varying in both emis- O or N atom and pyridine N atom
The development of intelligent mole- sion intensity and wavelength toward were identified as metal-chelating sites.
cules capable of performing logic oper- the tested metal ions Ni2 +, Cu2+, Zn2+, The fluorescence responses of 1d upon
ations would enable molecular-level Cd2+, Hg2+, and Pb2+ and the respons- metal chelation were employed for de-
devices and machines to be created. veloping truth tables for OR, NOR,
We designed a series of 2,5-diaryl-1,3,4- INHIBIT, and EnNOR logic gates as
Keywords: bidentate ligands · che-
oxadiazoles bearing a 2-(para-substitu- well as ON-OFF-ON and OFF-ON-
lates · fluorescence · metal ions ·
ted)phenyl and a 5-(o-pyridyl) group OFF fluorescent switches in a single
molecular devices
(substituent X=NMe2, OEt, Me, H, 1,3,4-oxadiazole molecular system.
Introduction vent polarity.[6] The tailored design of molecules exhibiting
multiple logic functions therefore remains to be explored. It
Molecular systems capable of performing logic operations appears that intelligent molecules with distinct coordina-
are attractive for the construction of molecular-level devices tion behavior could be potential candidates for the construc-
and machines that are in high demand in information tech- tion of novel logic operations,[7] which would allow the func-
nology.[1, 2] Since the first report of photonic molecular AND tions to be activated by the same kinds of metal-ion inputs.
logic gates,[3] logic systems consisting of chemically encoded We envisaged that a fluorescent ligand with varying metal-
information as input and a fluorescence signal as output chelating ability and chelating mode, with its emissive state
have received considerable attention and molecular systems capable of modulation as well, would allow multiple logic
showing functions such as AND, NAND, OR, NOR, XOR, gates to be created from a single fluorescent ligand by using
XNOR, and INHIBIT have been widely explored.[4, 5] How- individual metal ions or a combination of them as the input,
ever, relatively few molecular systems capable of performing with fluorescence output in terms of both intensity and
multiple logic functions of superior information processing wavelength.
capability have been reported.[6] In general, the reported 1,3,4-Oxadiazoles are organic molecules known for their
systems were based on the modulation of the emission prop- excellent optical properties, and are thus extensively exploit-
erties of the designed molecules by different combinations ed as signaling components in molecular sensory systems.[8]
of external inputs, such as metal ions, solution pH, and sol- We proposed to employ 1,3,4-oxadiazole as the molecular
framework for constructing multiple fluorescent logic gates
and switches. This was based on the conjugated structure of
2,5-diaryl-1,3,4-oxadiazole, such that its electronic distribu-
[a] Dr. A.-F. Li, Y.-B. Ruan, Q.-Q. Jiang, W.-B. He, Prof. Y.-B. Jiang
tion and emissive state can be modulated by varying the
Department of Chemistry, College of Chemistry
and Chemical Engineering
substituent at the 2-phenyl ring. Meanwhile, this structural
and the MOE Key Laboratory of Analytical Sciences
framework allows a bidentate metal-chelating environment
Xiamen University, Xiamen 361005 (China)
to be established when a metal binding site is incorporated
Fax: (+86) 592-2185662
into the 5-aryl ring. As the O and N atoms in the 1,3,4-oxa-
E-mail: ybjiang@xmu.edu.cn
diazole moiety can be respectively combined with this addi-
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200903265. tional binding site, two options of the bidentate chelation
5794 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2010, 16, 5794 5802
FULL PAPER
may be created. We therefore designed a series of 2,5- 1,3,4-oxadiazole fluorophore. This provides support to the
diaryl-1,3,4-oxadiazoles bearing a 2-(para-substituted)phenyl molecular design strategy that the electronic distribution
and a 5-(o-pyridyl) group (substituent X=NMe2, OEt, Me, may be tuned by substitution at the 2-phenyl ring and by
H, and Cl; 1a e, respectively; Scheme 1). The o-pyridyl metal chelation to the rest of the molecule as well.
Absorption and fluorescence spectra of 1: The absorption
spectra of 1a e were recorded in solvents of increasing po-
larity, namely, cyclohexane (CHX), diethyl ether (DEE),
ethyl acetate (EtOAc), dichloromethane (CH2Cl2), and ace-
tonitrile (CH3CN). Some of the spectral parameters are
summarized in Table S1 in the Supporting Information. In
general, the absorption of 1a and 1b e exhibits a major
band at 340 and 287 309 nm, respectively (Figure 2; Fig-
Scheme 1. Molecular structure of 2,5-diaryl-1,3,4-oxaA(thio)diazoles 1 3.
GNUNNERTGNUTHC
group at the C5 position of the oxadiazole ring was expected
to couple with the 1,3,4-oxadiazole ring to form an (O, N) or
(N, N) bidentate chelation environment for metal ions,
whereas the 2-phenyl group was introduced to test if the
electronic distribution and the emissive state could be tuned
by way of substitution. We found that the emission of 1a e
was indeed highly sensitive to the substitution, and the re-
sponse profiles in terms of emission intensity and wave-
Figure 2. Absorption spectra of 1a e (10 mm) in CH3CN.
length toward the tested metal ions Ni2 +, Cu2+, Zn2+, Cd2 +,
Hg2 +, and Pb2+ varied quite a lot, depending on the substi-
tuent X. On the basis of these observations, we developed a ures S1 S4 and Table S1 in the Supporting Information).
GNUNNERTGNUTHCA
unique molecular system capable of performing multiple The significantly redshifted absorption of 1a compared to
logic functions (OR, NOR, INHIBIT, and EnNOR) as well that of 1b e (Figure 2) is presumably due to the strong elec-
as ON-OFF-ON and OFF-ON-OFF fluorescent tron-donating ability of the NMe2 substituent. Molar absorp-
switches by simply varying the combination and level of tion coefficients at the 104 m 1 cm 1 order of magnitude are
metal-ion inputs in a single fluorescent ligand 1d. To the indicative of the p!p* transition character. It was found,
best of our knowledge, this is the first molecular system ca- from the data compiled in Table S1 (Supporting Informa-
pable of performing multiple logic functions based on the tion), that the absorption of 1 underwent a redshift with in-
1,3,4-oxadiazole fluorophore. creasing electron-donating ability of the substituent X in the
same solvent, whereas the absorption of 1 was insensitive to
the solvent polarity.
Results and Discussion The fluorescence of 1a e experiences a similar redshift
with increasing electron-donating ability of X in the same
Crystal structure of 1 b: Figure 1 shows the crystal structure solvent (Table S1 in the Supporting Information). However,
of 1b, which confirms the planar structure of the 2,5-diaryl- the emission of 1a e was found to be influenced by the sol-
vent polarity to an extent depending on X (Figure 3). The
emission of 1a shows a significant redshift with increasing
solvent polarity from 388 nm in CHX to 525 nm in CH3CN,
which is in contrast to the solvent-polarity-insensitive nature
of the absorption spectrum. This observation reveals that
the emissive state of 1a is of a charge-transfer (CT) type.
Upon the same variation of solvent, the emission of 1b and
1c shifts to the red by 39 and 13 nm, respectively, whereas
that of 1d and 1e hardly changes its position (Figure 3). The
observation that the solvatochromic effect becomes less and
less with decreasing electron-donating ability of X in 1 indi-
Figure 1. Crystal structure of 1b. cates that the CT in 1, if any, occurs from the X-substituted
Chem. Eur. J. 2010, 16, 5794 5802 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 5795
Y.-B. Jiang et al.
Table 1. Absorption and fluorescence spectral parameters of 1 and 3 in the
presence of 25 equivalents of metal ions in CH3CN.
Absorption Fluorescence
labs [nm] e [104 m 1 cm 1] Ks [105 m 1][a] lflu [nm] I/I0[b] F[c]
1a 235/284/ 1.27/1.11/3.35 525 0.477
343
1a+Ni2 + 293/320/ 1.52/1.74/2.35 >101 528 0.01 0.005
382
1a+Cu2 + 321/376/ 1.95/1.34/0.22 >101 526 0.002 0.024
630
1a+Zn2 + 292/320/ 1.50/1.79/2.22 1.27 0.043 529 0.08 0.022
378
1a+Cd2 + 292/325/ 1.40/1.88/1.99 0.21 0.005 526 0.21 0.074
366
1a+Hg2 + 296/325/ 1.62/2.11/1.85 >101 517 0.002 0.002
392
Figure 3. Normalized fluorescence spectra of 1a e (spectra a e, respec- 1a+Pb2 + 292/325/ 1.53/2.13/2.01 0.66 0.012 526 0.21 0.059
tively) in CHX (1), DEE (2), EtOAc (3), CH2Cl2 (4), and CH3CN (5). 371
1b 300 2.81 388 0.781
1b+Ni2 + 322 2.23 4.33 0.70 390 0.02 0.041
1b+Cu2+ 332 1.91 >101 390 0.005 0.007
2-phenyl group to the electron-deficient oxadiazole moiety.
1b+Zn2+ 315 2.18 0.38 0.007 508 0.65 0.511
Fluorescence quantum yields of 1 (Table S1 in the Support-
1b+Cd2+ 309 2.19 0.06 0.004 491 0.94 0.721
ing Information) were sensitive to the electronic character
1b+Hg2 + 329 1.85 >101 557 0.02 0.022
of X, too. For example, quantum yields in CHX decreased
1b+Pb2 + 314 2.01 0.28 0.006 389 0.19 0.385
dramatically from 0.71 (X=OEt) to 0.11 (Me), 0.015 (H), 1c 290 2.62 350 0.255
1c+Ni2 + 308 2.27 3.42 0.41 352 0.03 0.006
and 0.047 (Cl).
1c+Cu2 + 314 2.02 >101 350 0.01 0.004
All these spectral properties confirm that the fluorescence
1c+Zn2 + 301 2.27 0.28 0.005 414 2.8 0.721
of 1 is highly sensitive to the substituent X or the electronic
1c+Cd2 + 298 2.25 0.08 0.008 403 1.6 0.386
distribution in the whole molecule, and the emissive state of
1c+Hg2 + 312 1.90 >101 452 0.30 0.031
1c+Pb2 + 301 2.05 0.22 0.006 350 0.26 0.094
1 also undergoes variation with X. It was therefore expected
1d 287 2.57 334 0.015
that metal chelation to the bidentate structure formed by
1d+Ni2 + 301 2.30 1.42 0.049 338 0.08 0.002
1,3,4-oxadiazole and the 5-(o-pyridyl) moiety would act as
1d+Cu2+ 307 2.08 13.93 3.12 334 0.05 0.002
an alternative way of tuning the electronic distribution and
1d+Zn2+ 296 2.33 0.22 0.006 380 32.5 0.624
emission of the fluorescent ligands. In accordance with this 1d+Cd2+ 293 2.34 0.08 0.007 377 11.5 0.239
1d+Hg2 + 306 2.02 >101 416 0.42 0.009
assumption, we observed that the fluorescence quantum
1d+Pb2 + 296 2.07 0.18 0.004 334 0.56 0.009
yield of 1d in CH3CN (0.015) was much lower than that
1e 289 2.94 337 0.044
(0.83) of its model compound 2, in which the 5-(o-pyridyl)
1e+Ni2 + 303 2.60 1.24 0.055 341 0.09 0.002
moiety in 1d was replaced by a 5-phenyl group (Scheme 1).
1e+Cu2 + 310 2.33 11.66 2.75 344 0.04 0.002
1e+Zn2 + 299 2.63 0.17 0.004 390 10.3 0.537
This suggests that when a metal ion binds to the pyridine
1e+Cd2 + 293 2.64 0.03 0.003 387 4.0 0.194
N atom in 1d, for example, chelation-induced fluorescence
1e+Hg2 + 308 2.27 >101 429 0.15 0.011
enhancement would be observed. It was hence made clear
1e+Pb2 + 298 2.46 0.13 0.005 350 0.39 0.023
that the emission of a sophisticatedly chosen member of 1
3 308 2.51 375 0.029
could be employed to construct metal-ion-triggered molecu- 3+ Ni2 + 321 2.25 4.92 0.74 375 0.04 0.003
3+ Cu2 + 329 2.02 >101 375 0.01 0.003
lar logic gates or fluorescent switches.
3+ Zn2 + 319 2.26 0.32 0.008 403 4.4 0.121
3+ Cd2 + 311 2.33 0.035 0.003 395 2.3 0.059
Absorption and fluorescence spectra of 1 in the presence of
3+ Hg2 + 325 2.02 >101 424 0.41 0.013
metal ions: Interaction of 1 with metal ions was probed by
3+ Pb2 + 311 2.23 0.064 0.005 375 0.77 0.026
the absorption and fluorescence responses of 1 in CH3CN
[a] Binding constant of metal ion. [b] Fluorescence enhancement factor, the
toward the tested metal ions Ni2 +, Cu2+, Zn2+, Cd2+, Hg2 +,
ratio of fluorescence intensity in the presence of 25 equivalents of metal ion
(I) to that in the absence of the metal ion (I0). [c] Fluorescence quantum
and Pb2+ (Table 1). It was found that 1a e responded simi-
yields of 1a e and 3 in the presence of 25 equivalents of metal ion, measured
larly in their absorption spectra toward these metal ions
by referring to quinine sulfate standard.[10]
(Figures S5 S9 in the Supporting Information). The appear-
ance of isosbestic points in the titration traces suggested the
formation of well-defined binding complexes between 1a e found to differ very markedly. The CT fluorescence of 1a in
and the tested metal ions, which thereby allows their binding CH3CN was quenched by all the tested metal ions (Fig-
constants (Ks) to be fitted by a nonlinear fitting procedure ure S10 in the Supporting Information). In contrast, the
for a 1:1 binding complex[9] (Table 1). In general, the Ks fluorescence of 1c e was quenched by Ni2+, Cu2+, Hg2+,
values of 1a e in CH3CN became lower when substituent X and Pb2+, whereas it was enhanced by Zn2 + and Cd2+
was more electron-withdrawing. The fluorescence response (Figure 4 and Figures S11 S13 in the Supporting Informa-
profiles of 1a e toward these metal ions, however, were tion). With the latter two metal ions a redshifted new emis-
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Molecular Logic Gates and Switches
FULL PAPER
Figure 4. Fluorescence spectra of 1d (10 mm) in CH3CN in the presence of metal ions of increasing concentration. The concentration of metal ion in-
creased as indicated by the arrows in the same manner from 0 to 250 mm. The excitation wavelengths for acquiring the fluorescence spectra of the tested
metal ions Ni2 +, Cu2+, Zn2 +, Cd2 +, Hg2 +, and Pb2 + were the isosbestic wavelengths of 296, 300, 296, 297, 300, and 299 nm, respectively.
sion band appeared together with an isoemissive point. It that 1d among 1a e shows the most pronounced fluores-
was also found that the redshifted band of 1b e in the pres- cence responses toward metal ions (Figure 5). This fact indi-
ence of Zn2+ also depended on the substituent X (Fig- cates that a subtle balance of the electronic characters of
ure S14 in the Supporting Information). The fluorescence re- the 2- and 5-aryl groups is critical. Compound 1d was there-
sponse factors (I I0)/I0 of 1a e in the presence of 25 equiva- fore chosen for examining the logic functions. It should be
lents of a given metal ion are plotted in Figure 5. emphasized that other metal ions, such as Na+, Mg2+, and
The results presented in Figures 4 and 5 reveal rich pro- Ag+, were also tested and were found to exert practically
files of fluorescence response of 1 toward metal ions, in no influence on the absorption and fluorescence of 1d in
both intensity and wavelength. This again supports our mo- CH3CN (Figures S15 S17 in the Supporting Information).
lecular design of 1 and builds up the basis for constructing Related experiments were thereafter not continued on these
metal-ion-triggered logic gates and molecular switches using three metal ions.
1. Our systematic investigation thus leads to the observation
Coordination modes of 1 with metal ions: To probe the co-
ordination modes of 1 toward metal ions, the absorption and
fluorescence spectra of the tested molecule 1d and control
molecules 2 and 3 (Scheme 1) in CH3CN in the presence of
the tested metal ions were examined. The absorption and
fluorescence spectra of 2, which bears a 5-phenyl group
rather than the 5-(o-pyridyl) group in 1d, hardly showed
any response toward the metal ions (Figures S18 and S19 in
the Supporting Information), which indicates that the pyri-
dine N atom in 1d coordinates to the metal ions. With the
control compound 3 that bears a 1,3,4-thiodiazole instead of
the 1,3,4-oxadiazole in 1d, the fluorescence response to
Zn2+ in CH3CN was much weaker than that of 1d, whereas
its responses to Cu2+ and Hg2+ were similar to those of 1d
(Figure 6 and Figure S20 in the Supporting Information).
This finding suggests that the 1,3,4-oxadiazole O atom in 1d
Figure 5. a e) (I I0)/I0 of 1a e, respectively, in CH3CN in the presence of
25 equivalents of a given metal ion (250 mm). [1a e]=10 mm. dictates the fluorescence enhancement response of 1d
Chem. Eur. J. 2010, 16, 5794 5802 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 5797
Y.-B. Jiang et al.
Figure 6. Plots of fluorescence enhancement factor (I/I0) in CH3CN
versus concentration ratio of Zn2 + (a), Hg2 + (b), and Cu2+ (c) to 1d and
3. [1d]=[3] =10 mm.
toward Zn2+ but not Cu2 + and Hg2+. The slight difference
1
Figure 7. H NMR spectra of 1d (20 mm) in CD3CN in the presence of in-
in molecular structure of 1d and 3 may also contribute to
creasing equivalents of ZnA(ClO4)2. For proton numbering, see Scheme 2.
GNUNNERTGNUTHC
1
the observed difference in their fluorescence responses
A possible 2:1 1d Zn2 + complex was probed by H NMR spectroscopy,
presumably due to the much higher ligand concentration employed here
toward Zn2+. Calculations at the B3LYP/6-31G* level led to
than in the absorption and fluorescence spectral measurements at the
the optimized ground-state structures of 1d and 3 (Fig-
10 mm level. Job plots for the 1d Zn2 +(Cu2+) complex in CH3CN ob-
GNUNNERTGNUTHCA
ure S21 in the Supporting Information). The structure shows
tained by monitoring the fluorescence intensity data indicated a 1:1 bind-
that 1d is planar, whereas the 5-(o-pyridyl) ring in 3 is
ing stoichiometry (Figure S22 in the Supporting Information).
slightly twisted from the 2-phenyl-1,3,4-thiodiazole plane.
Presumably this could result from a larger repulsion be-
tween the S atom and pyridine N atom in 3 than that be- CH1 proton was shielded by the aryl ring current of 1d; at
tween the O atom and pyridine N atom in 1d. The X-ray higher Zn2+ concentrations, this 2:1 complex decomposed
crystal structure of 1b (Figure 1) agrees well with the calcu- into a 1:1 complex in which no shielding effect existed any
lated planar structure of 1. These findings indicate that the more (Scheme 2 a). It was therefore made clear that the
O atom in the 1,3,4-oxadiazole group of 1d possibly acts as CH1 proton behaved differently from others in the 5-pyridyl
the other binding site with Zn2 +. ring.[11] This observation helps to probe the coordination of
1
H NMR titrations of 1d by Zn2+ and Hg2 + in CD3CN Zn2+ with 1d at its pyridine N atom and oxadiazole O atom.
were carried out to better understand the coordination of In the case of Hg2+ titration, similar downfield shifts in the
1d with metal ions. The 5-pyridine proton signals of 1d signals of the CH2, CH3, and CH4 protons were observed.
were affected by the introduction of Zn2+ in that the signals The signal of the CH1 proton, however, behaved oppositely,
of protons CH1, CH2, CH3, and CH4 shifted significantly in that it shifted first to the downfield and then slightly to
(Figure 7). In contrast, all the 2-phenyl protons were only the upfield (Figure S23 in the Supporting Information).
slightly influenced by Zn2 + coordination. This titration Based on these observations, it was reasonable to conclude
result clearly confirmed the essential role of the pyridine that, although the pyridine N atom in 1d was a binding site
N atom in its coordination with
Zn2+. More importantly, the
signals of protons CH2, CH3,
and CH4 of the 5-pyridyl group
shifted significantly downfield
upon Zn2+ coordination,
whereas that of the CH1 proton
at the ortho position of the pyr-
idine N atom shifted upfield
upon the addition of 0.5 equiv-
alent of Zn2+ and thereafter
downfield (Figure 7). The shift
profile of the CH1 signal was
assumed to result from the ini-
tial formation of a 2:1 ligand
metal complex in which the Scheme 2. Proposed coordination modes of 1d with a) Zn2+ and b) Hg2+ and Cu2+.
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Molecular Logic Gates and Switches
FULL PAPER
for both Zn2+ and Hg2 +, the other coordination sites of 1d rescence intensity of 1d (10 mm) as a function of 5 equiva-
with Zn2+ and Hg2 + differed from each other. It was thus lents of Cu2+ (50 mm) and 5 equivalents of Hg2+ (50 mm) as
proposed that Hg2+ chelated to the pyridine N atom and the inputs is read as a NOR logic response. The truth table pre-
4-N atom in the 1,3,4-oxadiazole moiety of 1d, as shown in sented in Figure 9 indicates that the fluorescence of 1d ap-
pathway b in Scheme 2. The formation of a 2:1 1d Hg2 +
complex at a lower equivalent of Hg2+ was assigned to be
responsible for the downfield shift of the CH1 proton signal,
presumably due to an intermolecular hydrogen-bonding in-
teraction between this proton and the 3-N atom of the other
oxadiazole moiety. The proposed coordination of 1d with
Cu2+ (Scheme 2 b) agrees with that of a previously reported
relevant complex.[12]
Logic gating and switching behavior of 1 d with metal ions
as inputs: Different fluorescence outputs of 1b e, in particu-
lar 1d, upon the addition of the tested metal ions Ni2 +,
Cu2+, Zn2+, Cd2 +, Hg2+, and Pb2+ provide entries for devel-
oping molecular logic gates by using metal ions as inputs.
The fluorescence properties of 1d in the presence and ab-
sence of metal inputs were therefore employed to construct
Figure 9. Fluorescence spectra of 1d (10 mm) in CH3CN in the presence
molecular logic gates with the fluorescence enhancement of chemical inputs. [Cu2 + ]=[Hg2+ ]= 50 mm. The excitation wavelength
was 300 nm. The inset shows the logic table and the respective symbolic
factor (I/I0) as the threshold level. The OR gate is one of
representation of the NOR function.
the basic logic gates that implement logical disjunction,
which results in a high output (1) if one or both inputs to
the gate are high (1).[13] The fluorescence of 1d (10 mm),
which can be enhanced by Zn2+ or Cd2+ or both, enables pears at 334 nm (output 1 ) when neither Cu2+ nor Hg2+ is
the OR logic function when 1 equivalent of Zn2+ (10 mm) added, whereas it is quenched by applying one or both
and 5 equivalents of Cd2+ (50 mm) are taken as inputs inputs, which affords output 0 .
(Figure 8). The INHIBIT gate can be interpreted as a particular inte-
gration of AND and NOT logic gates such that the output
signal is inhibited by one of the active inputs.[15] A basic
two-input INHIBIT action can be obtained for 1d (10 mm)
with Zn2+ (10 mm) and Cu2+ (50 mm) as inputs. Enhancement
of 1d fluorescence is observed only in the presence of
1 equivalent of Zn2+ and the absence of Cu2 +, so that the
output is read as 1 . Under other circumstances the fluo-
rescence of 1d is quenched, thus leading to output 0 . The
corresponding truth table for the INHIBIT function is illus-
trated in Figure 10. It was therefore made clear that the IN-
Figure 8. Fluorescence spectra of 1d (10 mm) in CH3CN in the presence
of chemical inputs. [Zn2 + ]=10 mm, [Cd2 + ]=50 mm. The excitation wave-
length was 300 nm. The inset shows the logic table and the respective
symbolic representation of the OR function. I/I0 is the ratio of the fluo-
rescence spectrum area (310 520 nm) in the presence of metal ion to that
in the absence of the metal ion.
The NOR gate, as a universal gate that allows the combi-
natorial creation of all other Boolean operations, is of po-
tential interest.[14] A NOR gate, which integrates NOT and
OR logic gates, is performed only when neither of two
Figure 10. Fluorescence spectra of 1d (10 mm) in CH3CN in the presence
inputs is present. The combination of metal ions Ni2+, Cu2+,
of chemical inputs. [Zn2 + ]=10 mm, [Cu2 + ]=50 mm. The excitation wave-
Hg2 +, and Pb2+ as inputs leads to fluorescence quenching of
length was 300 nm. The inset shows the logic table and the respective
1d, and expresses the NOR logic function. The level of fluo- symbolic representation of the INHIBIT function.
Chem. Eur. J. 2010, 16, 5794 5802 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 5799
Y.-B. Jiang et al.
HIBIT function could be expanded to an enabled NOR
(EnNOR) logic gate by combining a NOR operator.[6j, 16]
Here, Zn2+ is a controlling input, which means that whenev-
er it is 1 the NOR gate works whereas this gate closes if it
is 0 . The corresponding logic circuit is depicted in Fig-
ure 11 b.
Figure 12. Outputs (I/I0) of 1d (10 mm) in CH3CN upon alternate addition
of Zn2 + and Cu2+: a) 5.0 mm Zn2 +, 25.0 mm Cu2 +, 50.0 mm Zn2 +, 150.0 mm
Cu2 +, 300.0 mm Zn2 +, 900.0 mm Cu2 + and b) 10.0 mm Cu2+, 10.0 mm Zn2+,
30.0 mm Cu2 +, 60.0 mm Zn2 +, 180.0 mm Cu2+, 360.0 mm Zn2+. The excita-
tion wavelength was 300 nm.
logic gates and switches. By modifying the substituent X at
the 2-phenyl group, we demonstrated that the electronic dis-
tribution and the emissive state of the molecule can be
modulated and that the emission depended sensitively on
the electronic distribution. The 5-(o-pyridyl) group was in-
corporated to form a bidentate coordination environment
with a 1,3,4-oxadiazole core, which creates two distinct coor-
dination modes for binding with different metal ions. 2,5-
Diaryl-1,3,4-oxadiazoles were shown to exhibit fluorescence
response profiles varying in both intensity and wavelength
toward metal ions such as Ni2+, Cu2+, Zn2+, Cd2+, Hg2+,
and Pb2+. This provides access to establish multiple logic
Figure 11. a) Fluorescence spectra of 1d (10 mm) in CH3CN in the pres-
functions in a single molecular system. OR, NOR, INHIBIT,
ence of chemical inputs. [Zn2+ ]=10 mm, [Cu2 + ]=[Hg2 + ]=50 mm.
and EnNOR logic gates as well as ON-OFF-ON and
b) The logic table and respective symbolic representation of the EnNOR
OFF-ON-OFF fluorescent switches were accordingly con-
function. The excitation wavelength was 300 nm.
structed from one derivative (1d) by varying the combina-
The rich fluorescence response profiles of 1d toward Zn2 + tions and levels of metal-ion inputs. It is expected that struc-
and Cu2+ also make it feasible to build up fluorescent tural modifications on 2- and/or 5-aryl moieties would
switches.[17] The fluorescence of 1d in CH3CN was enhanced create more structural motifs for extended design and appli-
upon addition of Zn2 +, whereas it was significantly cations in molecular intelligence , which is now under way
quenched by Cu2 +. Therefore, the fluorescent ON and in this laboratory.
OFF states can be modulated by the relative concentra-
tion of Zn2+ and Cu2 +. By setting I/I0>2.0 as the threshold
for the fluorescent ON state and I/I0<0.5 as that for the
Experimental Section
fluorescent OFF state, the fluorescent ON and OFF
states can be established by alternate addition of Zn2+ and
Materials: Chemicals used for synthesis were commercially available.
Cu2+. Sequential titration of 1d by Zn2 + and Cu2+ caused
CH3CN was of HPLC quality. CHX, DEE, EtOAc, CH2Cl2, and CH3CN
the fluorescence to be enhanced (ON) and quenched (OFF) for spectral studies were redistilled. Metal ions were used as their per-
chlorates. Solvents for NMR measurements had a deuteration grade of
(Figure 12). The fluorescent switches resulted from the com-
>99 atom D %. Compounds 1d,[18] 1e,[19] 2,[18] and 3[20] have been report-
petitive coordination of Zn2+ and Cu2+ with 1d that formed
ed in the literature.
1d Zn2+ and/or 1d Cu2+.
Measurements and methods: Absorption and fluorescence spectra were
recorded in a 1 cm quartz cell. All spectral titrations were carried out by
keeping the concentration of 1 3 constant (10 mm) while varying the
metal-ion concentrations (0 250 mm). The binding constants Ks were de-
Conclusion
termined from the absorbance in CH3CN at 25 8C. The absorbance data
were fitted to Equation (1),[9] in which A is the absorbance of the ligand
2,5-Diaryl-1,3,4-oxadiazoles bearing a 2-(para-substituted)-
in the presence of a given amount of metal ion, A0 is the absorbance of
phenyl and a 5-(o-pyridyl) group (substituent X= NMe2,
the initial solution of the free ligand, Alimit is the absorbance of full com-
OEt, Me, H, and Cl; 1a e) were designed for fluorescent plexation, and C0 and CM are the molar concentrations of ligand and
5800 www.chemeurj.org 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2010, 16, 5794 5802
Molecular Logic Gates and Switches
FULL PAPER
1
metal ion, respectively. Fluorescence quantum yields were measured 2-p-Tolyl-5-(pyridin-2-yl)-1,3,4-oxadiazole (1 c): H NMR (500 MHz,
using quinine sulfate as a standard (0.546 in 0.5 m H2SO4).[10] CDCl3, TMS): d=2.44 (s, 3 H), 7.33 (d, J= 8.0 Hz, 2 H), 7.46 (t, J=
6.0 Hz, 1 H), 7.89 (t, J =8.0 Hz, 1 H), 8.10 (d, J=7.0 Hz, 2 H), 8.31 (d, J =
13
8.0 Hz, 1 H), 8.81 ppm (d, J= 4.5 Hz, 1 H); C NMR (100 MHz, CDCl3,
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Alimit A0
TMS): d=21.6, 120.8, 123.1, 125.7, 127.2, 129.7, 137.1, 142.6, 143.7, 150.2,
AźA0þ cMþ1=Ksþc0 ðcMþ1=Ksþc0Þ2 4c0cM ð1Þ
2c0
163.6, 165.7 ppm; HRMS (ESI): m/z: calcd for C14H12N3O: 238.0980
[M+H+]; found: 238.0983 [M+H+].
1 13
1
H NMR (500 MHz) and C NMR (100 MHz) spectra were recorded in
2-Phenyl-5-(pyridin-2-yl)-1,3,4-oxadiazole (1 d): H NMR (500 MHz,
1
CDCl3 with TMS as an internal standard. H NMR (400 MHz) titrations
CDCl3, TMS): d=7.47 7.49 (m, 1 H), 7.52 7.57 (m, 3 H), 7.89 7.93 (m,
of 1d by Zn2 + and Hg2 + were carried out in CD3CN. HRMS spectra
1 H), 8.22 8.24 (m, 2 H), 8.32 (d, J=8.0 Hz, 1 H), 8.82 8.83 ppm (m, 1 H);
13
were obtained by using methanol as the solvent.
C NMR (100 MHz, CDCl3, TMS): d =123.3, 123.7, 125.8, 127.3, 129.0,
Single-crystal X-ray diffraction data were collected at 273 K. Absorption 132.0, 137.2, 143.7, 150.3, 163.9, 165.6 ppm; HRMS (ESI): m/z: calcd for
corrections were applied by using the multiscan program SADBS. The C13H10N3O: 224.0824 [M+H+]; found: 224.0817 [M+H+].
1
structure was solved by direct methods, and non-hydrogen atoms were
2-(4-Chlorophenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (1 e): H NMR
refined anisotropically by a least-squares method on F2 by using the
(500 MHz, CDCl3, TMS): d=7.47 7.50 (m, 1 H), 7.52 (d, 2 H, J=9.0 Hz,
SHELXTL-97 program. The hydrogen atoms were generated geometri-
2 H), 7.89 7.93 (m, 1 H), 8.16 (d, J =8.5 Hz, 2 H), 8.32 (d, J =7.5 Hz, 1 H),
13
cally (C H, 0.96 Š). CCDC-745239 (1b) contains the supplementary
8.82 ppm (d, J=4.5 Hz, 1 H); C NMR (100 MHz, CDCl3, TMS): d=
crystallographic data for this paper. These data can be obtained free of
122.1, 123.3, 125.9, 128.5, 129.4, 137.2, 138.3, 143.5, 150.3, 164.0,
charge from The Cambridge Crystallographic Data Centre via
164.8 ppm; HRMS (ESI): m/z: calcd for C13H9ClN3O: 258.0434 [M+H+];
www.ccdc.cam.ac.uk/data_request/cif.
found: 258.0434 [M+H+].
1
Geometry optimizations and vibrational analysis were performed by den-
2,5-Diphenyl-1,3,4-oxadiazole (2): H NMR (500 MHz, CDCl3, TMS): d=
13
sity functional theory with Becke s three-parameter hybrid exchange
7.52 7.57 (m, 6 H), 8.14 8.16 ppm (m, 4 H); C NMR (100 MHz, CDCl3,
functional and the Lee Yang Parr correlation functional (B3LYP) imple-
TMS): d= 123.9, 126.9, 129.1, 131.7, 164.6 ppm; HRMS (ESI): m/z: calcd
mented in the Gaussian 03 package. The 6-31G* basis set was used in all
for C14H11N2O: 223.0871 [M+H+]; found: 223.0875 [M+H+].
calculations.
1
2-Phenyl-5-(pyridin-2-yl)-1,3,4-thiadiazole (3): H NMR (500 MHz,
Preparation and characterization of 1 3: The substituted benzoyl chlo-
CDCl3, TMS): d =7.39 7.41 (m, 1 H), 7.51 7.52 (m, 3 H), 7.87 (t, J=
ride (2.2 mmol) in CH2Cl2 (10 mL) was added dropwise to a dried round
8.0 Hz, 1 H), 8.05 (t, J =3.5 Hz, 2 H), 8.40 (d, J= 8.0 Hz, 1 H), 8.68 ppm
13
flask containing picolinohydrazine or benzoyl hydrazine (2.0 mmol), pyri-
(d, J=5.0 Hz, 1 H); C NMR (100 MHz, CDCl3, TMS): d=121.0, 125.3,
dine (1.0 mL), and N,N-dimethyl-4-aminopyridine (DMAP; 60 mg) in di-
128.0, 129.2, 130.3, 131.2, 137.2, 149.2, 149.8, 169.9, 170.0 ppm; HRMS
chloromethane (15 mL). The mixture was stirred at room temperature
(ESI): m/z: calcd for C13H10N3S: 240.0595 [M+H+]; found: 240.0590
for 6 h and then washed with dilute aqueous HCl (1 m, 3 " 10 mL) and
[M+H+].
water (3 " 10 mL), and dried over sodium sulfate. After removal of the
solvent at reduced pressure, N -(4-substituted-benzoyl)picolinohydrazide
or N -benzoylbenzohydrazide was obtained as a white solid in 85 % yield,
and was directly used for the next step.
1 and 2 were respectively synthesized from N -(4-substituted-benzoyl)pi-
Acknowledgements
colinohydrazide and N -benzoylbenzohydrazide (1.5 mmol) by heating its
POCl3 (10 mL) solution at reflux for 6 h. After cooling, the solution was
This work was supported by the NSFC of China through grant nos.
poured into iced water and neutralized with saturated NaHCO3 solution.
J0630429, 20675069, and 20835005.
The resulting solution was extracted with CHCl3 (3 " 15 mL) and the or-
ganic phase was washed with water (3 " 15 mL) and saturated NaHCO3
solution (3 " 15 mL), and dried over sodium sulfate. After evaporation of
[1] V. Balzani, A. Credi, F. M. Raymo, J. F. Stoddart, Angew. Chem.
the solvent under reduced pressure, the residue was subjected to column
2000, 112, 3484 3530; Angew. Chem. Int. Ed. 2000, 39, 3348 3391.
chromatography on silica gel (ethyl acetate/petroleum ether, 1:3) to
[2] a) J. AndrØasson, U. Pischel, Chem. Soc. Rev. 2010, 39, 174 188;
afford 1 or 2 in 75 80 % yield.
b) K. Szacilowski, Chem. Rev. 2008, 108, 3481 3548; c) U. Pischel,
Compound 3 was synthesized by heating the solution of N -benzoylpicoli-
Angew. Chem. 2007, 119, 4100 4115; Angew. Chem. Int. Ed. 2007,
nohydrazide (1.5 mmol) and P2S5 (8 equiv) in pyridine (20 mL) to reflux.
46, 4026 4040; d) A. P. de Silva, S. Uchiyama, Nat. Nanotechnol.
After evaporation of the solvent under reduced pressure, water (30 mL)
2007, 2, 399 410; e) A. P. de Silva, N. D. McClenaghan, Chem. Eur.
was added and the mixture was extracted with CH2Cl2 (3 " 10 mL). The
J. 2004, 10, 574 586; f) F. M. Raymo, Adv. Mater. 2002, 14, 401
CH2Cl2 phase was washed with KOH (1 m, 3 " 10 mL) and then HCl (1 m,
414; g) A. P. de Silva, N. D. McClenaghan, Chem. Eur. J. 2002, 8,
3 " 10 mL), and dried over sodium sulfate. The solvent was removed
4935 4945.
under reduced pressure, and the crude product was purified by column
[3] A. P. de Silva, H. Q. N. Gunaratne, C. P. McCoy, Nature 1993, 364,
chromatography on silica gel (ethyl acetate/petroleum ether, 1:4) to
42 44.
afford 3 as a white solid in 60 % yield.
[4] For reviews, see: a) A. P. de Silva, T. P. Vance, M. E. S. West, G. D.
1
2-(4-Dimethylamino)-5-(pyridin-2-yl)-1,3,4-oxadiazole (1 a): H NMR
Wright, Org. Biomol. Chem. 2008, 6, 2468 2480; b) A. Credi,
(500 MHz, CDCl3, TMS): d= 3.07 (s, 6 H), 6.75 (d, J=9.0 Hz, 2 H), 7.42
Angew. Chem. 2007, 119, 5568 5572; Angew. Chem. Int. Ed. 2007,
7.45A(m, 1 H), 7.85 7.89 (m, 1 H), 8.06 (d, J=9.0 Hz, 2 H), 8.29 (d, J=
GNUNNERTGNUTHC
46, 5472 5475; c) D. C. Magri, T. P. Vance, A. P. de Silva, Inorg.
13
8.0 Hz, 1 H), 8.79 8.81 ppm (m, 1 H); C NMR (100 MHz, CDCl3, TMS):
Chim. Acta 2007, 360, 751 764; d) V. Balzani, A. Credi, M. Venturi,
d=40.0, 110.6, 111.5, 122.9, 125.3, 128.7, 137.0, 144.1, 150.1, 152.6, 162.8,
ChemPhysChem 2003, 4, 49 59; e) G. J. Brown, A. P. de Silva, S. Pa-
166.3 ppm; HRMS (ESI): m/z: calcd for C15H15N4O: 267.1246 [M+H+];
gliari, Chem. Commun. 2002, 2461 2463; f) A. P. de Silva, I. M.
found: 267.1241 [M+H+].
Dixon, H. Q. N. Gunaratne, T. Gunnlaugsson, P. R. S. Maxwell, T. E.
1
2-(4-Ethoxyphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (1 b): H NMR Rice, J. Am. Chem. Soc. 1999, 121, 1393 1394.
(500 MHz, CDCl3, TMS): d=1.46 (t, J=7.0 Hz, 3 H), 4.12 (q, J=7.0 Hz, [5] For some latest papers, see: a) P. Remón, R. Ferreira, J. M. Monte-
2 H), 7.01 (d, J =9.0 Hz, 2 H), 7.45 7.47 (m, 1 H), 7.88 7.91 (m, 1 H), 8.14 negro, R. Suau, E. PØrez-Inestrosa, U. Pischel, ChemPhysChem
(d, J=9.0 Hz, 2 H), 8.30 (d, J=8.0 Hz, 1 H), 8.80 8.82 ppm (m, 1 H); 2009, 10, 2004 2007; b) L. Mu, W. Shi, G. She, J. C. Chang, S. T.
13
C NMR (100 MHz, CDCl3, TMS): d= 14.7, 63.8, 114.9, 115.9, 123.1, Lee, Angew. Chem. 2009, 121, 3521 3524; Angew. Chem. Int. Ed.
125.6, 129.1, 137.1, 143.9, 150.2, 162.0, 163.4, 165.6 ppm; HRMS (ESI): 2009, 48, 3469 3472; c) R. Ferreira, P. Remón, U. Pischel, J. Phys.
m/z: calcd for C15H14N3O2: 268.1086 [M+H+]; found: 268.1083 [M+H+]. Chem. C 2009, 113, 5805 5811; d) N. Kaur, N. Singh, D. Cairns, J. F.
Chem. Eur. J. 2010, 16, 5794 5802 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 5801
Y.-B. Jiang et al.
Callan, Org. Lett. 2009, 11, 2229 2232; e) Z. Guo, P. Zhao, W. Zhu, [11] a) Ö. A. Bozdemir, O. Büyükcakir, E. U. Akkaya, Chem. Eur. J.
X. Huang, Y. Xie, H. Tian, J. Phys. Chem. C 2008, 112, 7047 7053; 2009, 15, 3830 3838; b) R. Dobrawa, M. Lysetska, P. Ballester, M.
Grüne, F. Würthner, Macromolecules 2005, 38, 1315 1325.
f) G. Zong, G. Lu, Tetrahedron Lett. 2008, 49, 5676 5679; g) X.
Chen, Z. Li, Y. Xiang, A. Tong, Tetrahedron Lett. 2008, 49, 4697 [12] P. Gómez-Saiz, J. García-Tojal, F. J. Arnµiz, M. A. Maestro, L.
Lezama, T. Rojo, Inorg. Chem. Commun. 2003, 6, 558 560.
4700.
[13] a) H. J. Jung, N. Singh, D. Y. Lee, D. O. Jang, Tetrahedron Lett. 2009,
[6] a) G. Q. Zong, G. X. Lu, J. Phys. Chem. C 2009, 113, 2541 2546;
50, 5555 5558; b) G. McSkimming, J. H. R. Tucker, H. Bouas-Lau-
b) S. Kumar, V. Luxami, R. Saini, D. Kaur, Chem. Commun. 2009,
rent, J. P. Desvergne, Angew. Chem. 2000, 112, 2251 2253; Angew.
3044 3046; c) C. H. Xu, W. Sun, Y. R. Zheng, C. J. Fang, C. Zhou,
Chem. Int. Ed. 2000, 39, 2167 2169; c) P. Ghosh, P. K. Bharadwaj, S.
J. Y. Jin, C. H. Yan, New J. Chem. 2009, 33, 838 846; d) Z. X. Li,
Mandal, S. Ghosh, J. Am. Chem. Soc. 1996, 118, 1553 1554.
L. Y. Liao, W. Sun, C. H. Xu, C. Zhang, C. J. Fang, C. H. Yan, J.
[14] a) A. Dhir, V. Bhalla, M. Kumar, Org. Lett. 2008, 10, 4891 4894;
Phys. Chem. C 2008, 112, 5190 5196; e) D. Zhang, J. H. Su, X. Ma,
b) M. Biancardo, C. Bignozzi, H. Doyle, G. Redmond, Chem.
H. Tian, Tetrahedron 2008, 64, 8515 8521; f) U. Pischel, B. Heller,
Commun. 2005, 3918 3920; c) Z. Wang, G. Zheng, P. Lu, Org. Lett.
New J. Chem. 2008, 32, 395 400; g) D. Margulies, C. E. Felder, G.
2005, 7, 3669 3672; d) B. Turfan, E. U. Akkaya, Org. Lett. 2002, 4,
Melman, A. Shanzer, J. Am. Chem. Soc. 2007, 129, 347 354; h) C. J.
2857 2859.
Fang, Z. Zhu, W. Sun, C. H. Xu, C. H. Yan, New J. Chem. 2007, 31,
[15] a) M. J. Yuan, W. D. Zhou, X. F. Liu, M. Zhu, J. B. Li, X. D. Yin,
580 586; i) W. Sun, Y. R. Zheng, C. H. Xu, C. J. Fang, C. H. Yan, J.
H. Y. Zheng, Z. C. Zuo, C. B. Ouyang, H. B. Liu, Y. L. Li, D. B.
Phys. Chem. C 2007, 111, 11706 11711; j) P. Singh, S. Kumar, New
Zhu, J. Org. Chem. 2008, 73, 5008 5014; b) A. Dhir, V. Bhalla, M.
J. Chem. 2006, 30, 1553 1556; k) Y. Shiraishi, Y. Tokitoh, T. Hirai,
Kumar, Tetrahedron Lett. 2008, 49, 4227 4230; c) M. Kluciar, R.
Chem. Commun. 2005, 5316 5318; l) S. H. Lee, J. Y. Kim, S. K.
Ferreira, B. de Castro, U. Pischel, J. Org. Chem. 2008, 73, 6079
Kim, J. H. Lee, J. S. Kim, Tetrahedron 2004, 60, 5171 5176; m) S.
6085; d) G. Nishimura, K. Ishizumi, Y. Shiraishi, T. Hirai, J. Phys.
Alves, F. Pina, M. T. Albelda, E. García-EspaÇa, C. Soriano, S. V.
Chem. B 2006, 110, 21596 21602; e) H. Miyaji, H. K. Kim, E. K.
Luis, Eur. J. Inorg. Chem. 2001, 405 412.
Sim, C. K. Lee, W. S. Cho, J. L. Sessler, C. H. Lee, J. Am. Chem.
[7] a) F. A. Khan, K. Parasuraman, K. K. Sadhu, Chem. Commun. 2009,
Soc. 2005, 127, 12510 12512.
2399 2401; b) Z. Q. Guo, W. H. Zhu, L. J. Shen, H. Tian, Angew.
[16] M. de Sousa, B. de Castro, S. Abad, M. A. Miranda, U. Pischel,
Chem. 2007, 119, 5645 5649; Angew. Chem. Int. Ed. 2007, 46, 5549
Chem. Commun. 2006, 2051 2053.
5553; c) A. Petitjean, N. Kyritsakas, J. M. Lehn, Chem. Eur. J. 2005,
[17] a) M. Kumar, R. Kumar, V. Bhalla, Chem. Commun. 2009, 7384
11, 6818 6828; d) K. Rurack, A. Koval chuck, J. L. Bricks, J. L. Slo-
7386; b) D. Zhang, Q. Zhang, J. Su, H. Tian, Chem. Commun. 2009,
minskii, J. Am. Chem. Soc. 2001, 123, 6205 6206.
1700 1702; c) S. H. Kim, J. S. Kim, S. M. Park, S. K. Chang, Org.
[8] a) Y. Liu, L. L. Zong, L. F. Zheng, L. G. Wu, Y. X. Cheng, Polymer
Lett. 2006, 8, 371 374; d) S. H. Kim, J. K. Choi, S. K. Kim, W. Sim,
2007, 48, 6799 6807; b) C. K. Kwak, C. H. Lee, T. S. Lee, Tetrahe-
J. S. Kim, Tetrahedron Lett. 2006, 47, 3737 3741.
dron Lett. 2007, 48, 7788 7792; c) S. H. Mashraqui, S. Sundaram,
[18] Yu. A. Efimova, T. V. Artamonova, G. I. Koldobskii, Russ. J. Org.
A. C. Bhasikuttan, Tetrahedron 2007, 63, 1680 1688; d) G. Zhou,
Chem. 2008, 44, 1345 1347.
Y. X. Cheng, L. X. Wang, X. B. Jing, F. S. Wang, Macromolecules
[19] D. M. Pore, S. M. Mahadik, U. V. Desai, Synth. Commun. 2008, 38,
2005, 38, 2148 2153. 3121 3128.
[9] B. Valeur, J. Pouget, J. Bourson, M. Kaschke, N. P. Ersting, J. Phys. [20] M. Santus, Acta Pol. Pharm. 1988, 45, 219 224.
Chem. 1992, 96, 6545 6549.
Received: November 30, 2009
[10] J. N. Demas, G. A. Crosby, J. Phys. Chem. 1971, 75, 991 1024.
Published online: April 9, 2010
5802 www.chemeurj.org 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2010, 16, 5794 5802
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