H. Wang et al. / Inorganica Chimica Acta 381 (2012) 111–116
115
is the first example of a naphthalimide-based ‘‘on–off’’ fluorescent
probe for Cu with significant color change.
was collected as a green oil (117 mg, 0.26 mmol, 42%); 1H NMR
(400 MHz, CDCl , 25 °C, TMS): d = 8.90 (m, 1H), 8.60 (m, 3H), 8.38
d, 1H), 7.71 (m, 1H), 7.59 (m, 2H; pyridyl), 7.36 (d, 2H; pyridyl),
2
+
3
(
7
2
.19 (m, 3H), 4.74 (s, 4H; CH
H; NCH CH ), 1.46 (m, 2H; CH
, 25 °C, TMS): d = 164.5, 164.0, 157.4, 153.6, 149.6,
36.7, 131.9, 131.1, 130.3, 130.1, 126.7, 125.9, 123.5, 122.5, 122.3,
17.6, 116.7, 59.9, 40.1, 30.3, 20.4, 13.9; MS (ESI): m/z: 451.2135
2
pyridyl), 4.18 (t, 2H; NCH
2
), 1.74 (m,
4
. Experimental
13
2
2
3
CH ), 0.98 (t, 3H; CH ); C NMR
2
3
(
400 MHz, CDCl
3
4.1. Materials
1
1
The salts used in stock solutions of metal ions were NaCl,
+
+
[
26 4 2
M+H ], 473.1950 [M+Na ]; Calc. for C28H N O : 450.2056.
CrCl
CuCl
AgNO
3
ꢂ6H
ꢂ6H
. Compound 3 was synthesized according to literature meth-
2
O, MnCl
2
ꢂ4H
2
O, FeCl
3
ꢂ6H
2
O, CoCl
2
ꢂ6H
2
O, NiCl
2
ꢂ6H
2
O,
2
2
O, Zn(NO
3
)
2
2
ꢂ6H O, CdCl
2
ꢂ2.5H
2
O, HgCl
2
, Pb(NO
3 2
) and
4
.3.3. Preparation of single crystal of complex 1–CuCl
To a solution of 1 (42 mg, 0.093 mmol) in CH
0 ml), CuCl in EtOH (20 mM, 4.6 ml) was added dropwise. After
2
3
2
2
Cl /EtOH (4:1,
od. Other chemicals were purchased from commercial sources. Sol-
vents were of analytical grade and purified by standard methods.
1
2
stirring for 30 min at room temperature and filtering, the solvent
was removed through evaporation. The residual was redissolved
in CH
4.2. General methods
3
CN (6 ml). After standing for 2 days, the green crystal was
obtained.
1H and 13C NMR spectra were recorded on a Bruker 400 MHz
NMR spectrometer and the chemical shifts were reported in ppm
in CDCl , TMS as internal standard). ESI mass spectra were re-
4.4. Absorption and fluorescence response experiments
(
3
corded on a Varian/Ionspec QFT-7 Fourier-transform ion-cyclo-
tron-resonance (FT-ICR) mass spectrometer with a Micromass
Z-spray ESI ion source. Absorption spectra were measured on HIT-
ACHI U-4100 spectrophotometer. Fluorescence emission spectra
were measured on an ISS K2 system. Single crystal of the complex
for X-ray diffraction analysis with suitable dimensions was
mounted on a glass rod, and the crystal data were collected on a
Stock solutions (0.5 mM) of each metal salts, probe 1 (0.2 mM)
in acetonitrile were prepared. Test solutions were prepared by
placing 1 ml of the probe’s stock solutions into a test tube, adding
an appropriate aliquot of each metal stock solution, and then dilut-
ing the solution to 10 ml with acetonitrile and 2 ml distilled water
to give the final concentration. After complete mixing for 10 min,
measurements of UV–Vis absorption and fluorescent emission
were carried out on above mentioned spectrophotometers with a
Bruker SMART CCD diffractometer with a Mo K
a sealed tube
(
k = 0.71073 Å) at 293 K, using the scan mode. The structure
x
1
cm standard quartz cell.
solution and refinement of the data were handled with the SHEL-
XS-86 and SHELXL-97 programs.
Acknowledgments
4
4
.3. Preparation
Financial support from the Natural Science Foundation of China
Grant Nos. 21073112, 20771066), Key Lab of Photochemistry of
Chinese Academy of Science, and Shandong University are grate-
fully acknowledged. H. Wang thanks Science and Technology
Department of Henan Province for support under its ‘‘Program for
Research in Basic and Frontier Technology’’ (No. 092300410193).
(
.3.1. Synthesis of N-n-butyl-4-(2-pyridylmethyl)amino-1,8-
naphthalimide (2)
To a solution of 3 (1 g, 3.32 mmol) in 2-methoxyethanol (40 ml),
-aminomethyl pyridine (900 mg, 8.32 mmol) was added at room
2
temperature. After reflux for 24 h, the cooled reacting mixture
was dissolved in dichloromethane and washed with water. The col-
lected organic phase was dried over anhydrous MgSO . After evap-
4
Appendix A. Supplementary material
oration of solvent, the crude product was purified by column
chromatography on silica gel (200–300 mesh) using 1000:6 (v/v)
CHCl
3
/MeOH as eluent, compound 2 (845 mg, 2.35 mmol) was ob-
1
tained as yellow solid in 78% yield; H NMR (400 MHz, CDCl
3
,
References
2
1
5 °C, TMS): d = 8.68 (d, 1H), 8.60 (m, 1H), 8.48 (d, 1H), 8.33 (d,
H), 7.76 (m, 1H), 7.67 (m, 1H), 7.37 (d, 1H), 7.30 (m, 1H), 7.18
[
1] (a) A.W. Czarnik, Fluorescent Chemosensors for Ion and Molecule Recognition,
A.C.S., Washington, DC, 1992;
(
b, 1H; NH), 6.73 (d, 1H), 4.67 (d, 2H; NHCH
2
), 4.18 (t, 2H; NCH
2
),
);
(
b) C.D. Geddes, J.R. Lakowicz, Advanced Concepts in Fluorescence Sensing Part
A: Small Molecule Sensing, Springer, New York, 2005;
c) A.P. de Silva, H.Q.N. Gunaratne, T. Gunnlaugsson, A.J.M. Huxley, C.P. McCoy,
J.T. Rademacher, T.E. Rice, Chem. Rev. 97 (1997) 1515;
1
.72 (m, 2H; NCH
2
CH
2
), 1.46 (m, 2H; CH
3
CH
2
), 0.98 (t, 3H; CH
3
1
3
3
C NMR (400 MHz, CDCl , 25 °C, TMS): d = 165.0, 164.2, 155.1,
(
1
1
3
C
53.7, 149.1, 148.9, 136.9, 136.6, 134.4, 131.1, 129.8, 126.4,
(
(
(
d) A.P. de Silva, D.B. Fox, A.J.M. Huxley, T.S. Moody, Coord. Chem. Rev. 205
2000) 41;
e) C. Bargossi, M.C. Fiorini, M. Montalti, Prodi L. Prodi, N. Zaccheroni, Coord.
24.8, 123.2, 122.8, 122.3, 121.9, 120.6, 110.7, 104.7, 47.4, 39.9,
+
0.3, 20.4, 13.9; MS (ESI): m/z: 360.1734 [M+H ]; Calc. for
22
H
21
N
3
O
3
: 359.1634.
Chem. Rev. 208 (2000) 17;
(
(
f) L.F. Bolletta, M. Montalti, N. Zaccheroni, Coord. Chem. Rev. 205 (2000) 59;
g) D.T. McQuade, A.E. Pullen, T.M. Swager, Chem. Rev. 100 (2000) 2537;
4.3.2. Synthesis of N-n-butyl-4-di(2-pyridylmethyl)amino-1,8-
(h) K. Rurack, Spectrochim. Acta, Part A 57 (2001) 2161;
(
(
(
i) P. Jiang, Z. Guo, Coord. Chem. Rev. 248 (2004) 205;
j) J.F. Callan, A.P. de Silva, D.C. Magri, Tetrahedron 61 (2005) 8551;
k) T. Gunnlaugsson, M. Glynn, G.M. Tocci (née Hussey), P.E. Kruger, F.M. Pfeffer,
naphthalimide (1)
A mixture of 2-chloromethylpyridine hydrochloride (450 mg,
2
.74 mmol), compound 3 (220 mg, 0.62 mmol), hexadecyltrimethy-
lammonium chloride (400 mg) and anhydrous potassium carbonate
500 mg) in acetonitrile (50 mL) was refluxed for 24 h. After the sol-
Coord. Chem. Rev. 250 (2006) 3094;
(l) J.S. Kim, D.T. Quang, Chem. Rev. 107 (2007) 3780;
(
m) E.M. Nolan, S.J. Lippard, Chem. Rev. 108 (2008) 3443.
2] (a) A.P. de Silva, T. Gunnlaugsson, T.E. Rice, Analyst 121 (1996) 1759;
b) A.P. de Silva, H.Q.N. Gunaratne, T. Gunnlaugsson, C.P. McCoy, P.R.S. Maxwell,
J.T. Rademacher, T.E. Rice, Pure Appl. Chem. 68 (1996) 1443;
(
[
vent was evaporated, the residue was dissolved in dichloromethane
and washed with water. The collected organic phase was dried over
(
(
(
(
c) A.P. de Silva, H.Q.N. Gunaratne, C.P. McCoy, Chem. Commun. (1996) 2399;
d) R. Krämer, Angew. Chem., Int. Ed. 37 (1998) 772;
e) L. Fabbrizzi, M. Licchelli, L. Parodi, A. Poggi, A. Taglietti1, J. Fluorine 8 (1998)
anhydrous MgSO
product was purified by column chromatography on silica gel (200–
00 mesh) using 200:3 (v/v) CHCl /MeOH as eluent. Compound 1
4
. After evaporation of solvent, the brownish crude
3
3
263;