The synthesis, X-ray crystal structure and optical properties of novel 1-ferrocenyl-2-(3-phenyl-1H-1,2,4-triazol-5-ylthio)ethanone derivatives

Article abstract of DOI:10.1016/j.saa.2010.04.019

A series of novel 1-ferrocenyl-2-(3-phenyl-1H-1,2,4-triazol-5-ylthio)ethanone derivatives was synthesized by the reaction of 3-substituted-1H-1,2,4-triazole-5-thiol and chloroacetyl ferrocene in the presence of sodium hydride and potassium iodide at reflux. The structures of the new compounds were determined by IR and ¹H NMR spectroscopy and HRMS. The structure of compound 5c was established by X-ray crystallography. UV-vis absorption and fluorescence spectra were recorded in ethanol and dichloromethane. The results showed that compounds 5a-g display similar absorptions ranging from 300 to 500 nm and maximal emission bands are about 566 nm. The intensity of fluorescence and maximal emission bands are dependent on the groups bonded to triazole rings.

Full text of DOI:10.1016/j.saa.2010.04.019

Spectrochimica Acta Part A 76 (2010) 531–536
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
The synthesis, X-ray crystal structure and optical properties of novel
1-ferrocenyl-2-(3-phenyl-1H-1,2,4-triazol-5-ylthio)ethanone derivatives
Wei-Yong Liua, Yong-Sheng Xiea,c, Bao-Xiang Zhaoa,∗, Song Liana, Hong-Shui Lva,
Zhong-Liang Gonga, Dong-Soo Shinb
a Institute of Organic Chemistry, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, PR China
b Department of Chemistry, Changwon National University, Changwon 641-773, South Korea
c Department of Chemical and Environment Engineering, Chongqing Three Gorges University, Chongqing 404000, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of novel 1-ferrocenyl-2-(3-phenyl-1H-1,2,4-triazol-5-ylthio)ethanone derivatives was syn-
thesized by the reaction of 3-substituted-1H-1,2,4-triazole-5-thiol and chloroacetyl ferrocene in the
presence of sodium hydride and potassium iodide at reflux. The structures of the new compounds were
determined by IR and 1H NMR spectroscopy and HRMS. The structure of compound 5c was established
by X-ray crystallography. UV–vis absorption and fluorescence spectra were recorded in ethanol and
dichloromethane. The results showed that compounds 5a–g display similar absorptions ranging from
300 to 500 nm and maximal emission bands are about 566 nm. The intensity of fluorescence and maximal
emission bands are dependent on the groups bonded to triazole rings.
Received 19 January 2010
Received in revised form 14 April 2010
Accepted 15 April 2010
Keywords:
1,2,4-Triazole
Ferrocene
Synthesis
X-ray
© 2010 Elsevier B.V. All rights reserved.
UV-vis absorption
Fluorescence
1. Introduction
molecule has been recognized as an attractive way to endow a
novel molecule functionally [19–21]. In the electroluminescence
1,2,4-Triazoles and their condensed derivatives constitute an
important class of organic compounds with bioactivities such as
analgesic–anti-inflammatory [1], antimicrobial [2,3], anticancer
[4,5], antifungal [6], antigenotoxic [7], herbicidal [8], and insec-
ticidal activities [9]. In addition, 1,2,4-triazole and, in particular,
its derivatives are very interesting as ligands [10–12], which have
the potential possibility of coordinating with metal ions to fulfill
the coordination requirements of clusters. In recent years, 1,2,4-
triazole and its derivatives have been paid great attention in the
field of electroluminescence [13–17]. The design and synthesis of
fluorescent chemosensors with desirable properties is of consider-
able current interest in biology research. The advent of sensitive
fluorescence detectors has enabled advances in biological imag-
ing and the emergence of the field of single molecule spectroscopy
[18].
research, ferrocene derivatives have also attracted much atten-
tion with respect to their high degree of chemical and thermal
stabilities, electrochemical, electronic, and magnetic properties
[22–26].
To date there have been relatively few studies on the cellu-
lar localization of agents in which a small molecule is linked to
a fluorophore, such as coumarin [27,28]. Thus, in continuation of
our efforts in synthesizing various bioactive molecules [29–32], we
would like to synthesize novel small molecules with both poten-
tial bioactivity and fluorescent property. We report, herein, the
synthesis, X-ray crystal structure and optical properties of novel
1-ferrocenyl-2-(3-phenyl-1H-1,2,4-triazol-5-ylthio)ethanone.
2. Materials and methods
Incorporation of a ferrocene fragment into a molecule of an
organic compound often obtained unexpected biological activity,
which is rationalized as being due to their different membrane
permeation properties and anomalous metabolism. The integra-
tion of one or more ferrocene units into a heterocyclic ring
2.1. General
Thin-layer chromatography (TLC) was conducted on silica gel
60 F254 plates (Merck KGaA). 1H NMR spectra were recorded on a
Bruker Avance 400 (400 MHz) spectrometer, using CDCl3 as solvent
and tetramethylsilane (TMS) as internal standard. Melting points
were determined on an XD-4 digital micromelting point apparatus.
IR spectra were recorded with an IR spectrophotometer VERTEX
70 FT-IR (Bruker Optics). HRMS spectra were recorded on a Q-
∗
Corresponding author. Tel.: +86 531 88366425; fax: +86 531 88564464.
E-mail addresses: bxzhao@sdu.edu.cn, sduzhao@hotmail.com (B.-X. Zhao).
1386-1425/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2010.04.019

532
W.-Y. Liu et al. / Spectrochimica Acta Part A 76 (2010) 531–536
Fig. 1. Synthesis of 1-ferrocenyl-2-(3-substituted-1H-1,2,4-triazol-5-ylthio)ethanone.
TOF6510 spectrograph (Agilent). UV–vis spectra were recorded on
a U-4100 (Hitachi). Fluorescent measurements were recorded on a
Perkin–Elmer LS-55 luminescence spectrophotometer.
2.4.2. 1-Ferrocenyl-2-(3-(furan-2-yl)-1H-1,2,4-triazol-5-
ylthio)ethanone (5b)
Orange solid, yield 73%; mp 139–142 ◦C; IR (KBr, cm−1): 3245,
1662; 1H NMR(CDCl3, 400 MHz), ı: 11.73 (s, 1H, NH triazole), 7.52
(s, 1H, furan), 7.01 (d, J = 3.3 Hz, 1H, furan), 6.51 (t, J = 1.4 Hz, 1H,
furan), 4.87 (t, J = 1.7 Hz, 2H, Cp), 4.64 (d, J = 1.7 Hz, 2H, Cp), 4.28 (s,
7H, Cp and COCH2S); HRESIMS calcd for [M+H]+ C18H16FeN3O2S:
394.0313, found: 394.0303.
2.2. General procedure for the synthesis of
3-substituted-1H-1,2,4-triazole-5-thiol (4a–g)
As shown in Fig. 1, compound 4 was synthesized according to the
literature method [33,34]. 2-(Acetyl)hydrazinecarbothioamide or
2-(4-aroyl)hydrazinecarbothioamide (3) (10 mmol) and 5% sodium
hydroxide aqueous (40 mL) were added to a three-necked round-
bottomed flask. The mixture was refluxed for 2–3 h, and then it was
cooled to room temperature. The mixture was acidified with acetic
acid to about pH 5. After filtration, the solid was washed with cold
water and dried to afford 3-substituted-1H-1,2,4-triazole-5-thiol
(4) in 77–90% yield.
2.4.3. 1-Ferrocenyl-2-(3-phenyl-1H-1,2,4-triazol-5-ylthio)ethanone
(5c)
Orange solid, yield 57%; mp 156–159 ◦C; IR (KBr, cm−1): 3226,
1666; 1H NMR (CDCl3, 400 MHz), ı: 11.84 (s, 1H, NH triazole), 8.04
(s, 2H, Ar), 7.42 (s, 3H, Ar), 4.88 (s, 2H, Cp), 4.65 (s, 2H, Cp), 4.27
(s, 7H, Cp and COCH2S); HRESIMS calcd for [M+H]+ C20H18FeN3OS:
404.0520, found: 404.0513.
2.4.4. 1-Ferrocenyl-2-(3-p-tolyl-1H-1,2,4-triazol-5-ylthio)ethanone
(5d)
2.3. General procedure for the synthesis of
1-ferrocenyl-2-(3-substituted-1H-1,2,4-triazol-5-ylthio)ethanone
(5a–f)
Brown solid, yield 73%; mp 178–182 ◦C; IR (KBr, cm−1): 3163,
1656; 1H NMR (CDCl3, 400 MHz), ı: 11.99 (s, 1H, NH triazole), 7.91
(d, J = 7.8 Hz, 2H, Ar), 7.23 (d, J = 7.8 Hz, 2H, Ar), 4.87 (s, 2H, Cp),
4.62 (s, 2H, Cp), 4.30 (s, 2H, COCH2S), 4.26 (s, 5H, Cp), 2.38 (s, 3H,
CH3); HRESIMS calcd for [M+H]+ C21H20FeN3OS: 418.0677, found:
418.0643.
To a round-bottomed flask 3-substituted-1H-1,2,4-triazole-5-
thiol (4) (1.25 mmol), sodium hydride (60% dispersion in mineral
oil, 120 mg, 2.85 mmol), potassium iodide (190 mg, 1.14 mmol),
chloroacetyl ferrocene (300 mg, 1.14 mmol) and toluene (30 mL)
were added and the mixture was refluxed for 3–4 h. The reaction
mixture was cooled and poured into cold water (25 mL). The mix-
ture was extracted with ethyl acetate (3× 30 mL), and then the
combined extraction was dried over anhydrous magnesium sulfate.
After filtration, the solvent was removed under reduced pressure
in a rotary evaporator. The crude residue was purified by column
chromatography on silica gel to afford compound 5a–f in 57–87%
yield.
2.4.5. 1-Ferrocenyl-2-(3-(4-methoxyphenyl)-1H-1,2,4-triazol-5-
ylthio)ethanone (5e)
Red brown solid, yield 87%; mp 175–178 ◦C; IR (KBr, cm−1):
3184, 1653; 1H NMR(CDCl3, 400 MHz), 11.85 (s, 1H, NH triazole), ı:
7.95 (d, J = 6.0 Hz, 2H, Ar), 6.95 (d, J = 7.1 Hz, 2H, Ar), 4.87 (s, 2H, Cp),
4.63 (s, 2H, Cp), 4.29 (s, 2H, COCH2S), 4.26 (s, 5H, Cp), 3.84 (s, 3H,
CH3); HRESIMS calcd for [M+H]+ C21H20FeN3O2S: 434.0626, found:
434.0613.
2.4. Data of compounds 5
2.4.6. 1-Ferrocenyl-2-(3-(3-bromophenyl)-1H-1,2,4-triazol-5-
ylthio)ethanone (5f)
2.4.1. 1-Ferrocenyl-2-(3-methyl-1H-1,2,4-triazol-5-ylthio)ethanone
(5a)
Yellow solid, yield 80%; mp 154–156 ◦C; IR (KBr, cm−1): 3247,
1665; 1H NMR (CDCl3, 400 MHz), ı: 12.12 (s, 1H, NH triazole), 8.25
(s, 1H, Ar), 8.00 (d, J = 6.1 Hz, 1H, Ar), 7.52 (d, J = 7.4 Hz, 1H, Ar), 7.30
(t, J = 6.9 Hz, 1H, Ar), 4.88 (s, 2H, Cp), 4.68 (s, 2H, Cp), 4.27 (s, 5H, Cp),
4.22 (s, 2H, COCH2S); HRESIMS calcd for [M+H]+ C20H17BrFeN3OS:
481.9625, found: 481.9611.
Dark brown solid, yield 85%; mp 124–128 ◦C; IR (KBr, cm−1):
3228, 1664; 1H NMR (CDCl3, 400 MHz), ı: 11.22 (s, 1H, NH triazole),
4.85 (s, 2H, Cp), 4.60 (s, 2H, Cp), 4.26 (s, 7H, Cp and COCH2S), 2.45
(s, 3H, CH3); HRESIMS calcd for [M+H]+ C15H16FeN3OS: 342.0363,
found: 342.0355.

W.-Y. Liu et al. / Spectrochimica Acta Part A 76 (2010) 531–536
533
2.4.7. 1-Ferrocenyl-2-(3-(4-nitrophenyl)-1H-1,2,4-triazol-5-
ylthio)ethanone (5g)
A 100 mL, three-necked, round-bottomed flask was fitted with
a magnetic stir bar. Under nitrogen, the flask is charged with 3-(4-
nitrophenyl)-1H-1,2,4-triazole-5-thiol (4 g) (279 mg, 1.25 mmol),
sodium hydride (60% dispersion in mineral oil, 120 mg, 2.85 mmol),
potassium iodide (190 mg, 1.14 mmol), chloroacetyl ferrocene
(300 mg, 1.14 mmol), toluene (30 mL) and DMF (6 mL). The mix-
ture was stirred and refluxed for 2 h. The reaction mixture was
cooled to room temperature, and poured into water (25 mL). The
mixture was extracted with ethyl acetate (3× 30 mL), and then the
combined extraction was dried over anhydrous magnesium sulfate.
After filtration, the solvent was removed under reduced pressure
in a rotary evaporator. The crude residue was purified by column
chromatography (silica gel; 1:2 petroleum ether—ethyl acetate) to
afford brown solid (121 mg), yield 24%; mp 189–192 ◦C; IR (KBr,
cm−1): 3348, 3099, 3086, 1651; 1H NMR (CDCl3, 400 MHz), ı: 12.29
(s, 1H, NH triazole), 8.28 (s, 4H, Ar), 4.88 (s, 2H, Cp), 4.71 (s, 2H, Cp),
4.28 (s, 5H, Cp), 4.19 (s, 2H, COCH2S); HRESIMS calcd for [M+H]+
C20H17FeN4O3S: 449.0371, found: 449.0360.
2.5. X-ray crystallography
Suitable single crystals of 5c for X-ray structural analysis were
obtained by slow evaporation of a solution of the solid in ace-
tone. The diffraction data for structure was collected with a Bruker
SMART CCD diffractometer using a graphite monochromated Mo
K␣ radiation (ꢀ = 0.71073 Å) at 298(2) K. The structure was solved
by direct methods with SHELXS-97 program and refinements on
F2 were performed with SHELXL-97 program by full-matrix least-
squares techniques with anisotropic thermal parameters for the
nonhydrogen atoms. All H atoms were initially located in a dif-
ference Fourier map. The methyl H atoms were then constrained
to an ideal geometry, with C–H = 0.96 Å and Uiso(H) = 1.5 Ueq(C). All
other H atoms were placed in geometrically idealized positions and
constrained to ride on their parent atoms, with C–H = 0.93 Å and
Uiso(H) = 1.2Ueq(C).
Fig. 2. The molecular structure of compound 5c, with displacement ellipsoids drawn
at the 50% probability level and H atoms omitted.
instrument in present conditions except 5b for which a triplet and
a doublet peaks were observed as normal monosubstituted Cp ring.
Five protons of unsubstituted Cp appeared around 4.27 ppm as sin-
glet peak. Two methylene protons appeared around 4.20–4.30 ppm
as singlet peak. It is interesting that the signal of methylene protons
was upfield when benzene moiety possesses electron-withdrawing
substituent, whereas it was downfield in the case of electron-
donating substituent, comparing the signal of unsubstituted Cp.
3. Result and discussion
3.3. X-ray crystallography
3.1. Synthesis
The spatial structure of compound 5c was determined by using
X-ray diffraction analysis. Crystals suitable for X-ray diffraction
were obtained by slow evaporation of a solution of the solid in
acetone at room temperature for 7 days. The molecular view of
5c is shown in Fig. 2. A summary of crystallographic data collec-
tion parameters and refinement parameters for 5c are compiled in
Table 1.
The synthetic approach for the preparation of 1-ferrocenyl-
2-(3-substituted-1H-1,2,4-triazol-5-ylthio)ethanone derivatives is
shown in Fig. 1. Firstly, the acyl thiosemicarbazide 3 was obtained
by the reaction of acetyl chloride or aroyl chloride 1 and thiosemi-
carbazide 2, which are readily available, in the presence of pyridine
at 0 ◦C [34]. Compound 3 was cyclized with 5% aqueous sodium
hydroxide to afford 3-substituted-1H-1,2,4-triazole-5-thiol 4 in
good yield after work-up. Finally compound 4 reacted with
chloroacetyl ferrocene in toluene in the presence of sodium hydride
and potassium iodide at reflux for 3–4 h to furnish 1-ferrocenyl-
2-(3-substituted-1H-1,2,4-triazol-5-ylthio)ethanone 5 in 24–87%
yield.
Fig. 2 shows that compound 5c contains a phenyl ring bonded
to the triazole ring which links a ferrocenyl group by a flexible
S–C–C O chain. In the ferrocenyl moiety, the cyclopentadienyl (Cp)
rings are perfectly planar but deviate slightly from being paral-
lel, that is, the angle between the planes is 2.9(4)◦, and two Cp
rings twist from the eclipsed conformation by 27.23–28.50◦. The
angle Cg1–Fe1–Cg2 is 176.52(13)◦. Cg1 and Cg2 is the centroid of
unsubstituted Cp ring and substituted Cp ring, respectively. The
distances Cg1–Fe and Cg2–Fe are 1.647(3) and 1.642(2) Å. The C–C
bond lengths and C–C–C angles in the cyclopentadienyl rings show
electronic overlap of the p-system-induced variations. The triazole
ring makes dihedral angles of 3.6(3)◦ and 77.8(3)◦ with the bonded
phenyl ring and the substituted Cp ring, respectively. In the crystal,
molecules are connected via pairs of intermolecular N3–H1. . .O1
hydrogen bonds into inversion dimers and further assembled into
(0 0 1) layers via stacking interactions between the phenyl ring and
the triazole ring [interplanar distance = 3.642(3) Å] (Table 2). Fur-
thermore, the crystal is consolidated by another intermolecular
3.2. Structure characterization
The structures of the products 5 were determined by the anal-
yses of their spectral data including IR, 1H NMR and HRMS. The
IR spectra of all the compounds 5a–g showed ꢁ(C O) stretch at
1651–1666 cm−1 consisting with carbonyl. In the 1H NMR spec-
tra, the signal of a proton in triazole moiety appeared at the
range of ı 11.22–12.29 ppm and it was downfield as increase
of electron-withdrawing in the benzene moiety. Four protons in
monosubstituted Cp of Fc moiety peaks appeared around 4.87 and
4.65 ppm as singlet that maybe results from resolving power of

534
W.-Y. Liu et al. / Spectrochimica Acta Part A 76 (2010) 531–536
Table 1
Table 2
Summary of crystallographic data and structure refinement details for 5c.
Hydrogen bond geometry (Å,◦).
5c
D–H. . .Aa
D–H
H. . .A
D. . .A
D–H. . .A
Empirical formula
Formula weight
Temperature
C20H17FeN3OS
403.28
298(2) K
N3–H1. . .O1i
0.86
0.98
0.93
2.11
2.45
2.86
2.935(5)
3.408(6)
3.777(7)
159
166
167
C4–H4. . .N2ii
C18–H18. . .Cg1iii
Wavelength
Crystal system
Space group
0.71073 Å
Triclinic
P-1
D and A are the hydrogen bond donor and acceptor, respectively.
a
Symmetry code: (i) 1 − x, 1 − y, −z; (ii) 1 + x, 1 + y, 1 + z; (iii) 1 − x, −y, 1 − z.
Unit cell dimensions
a = 9.755(4) Å, ˛ = 104.142(6)◦
b = 10.347(4) Å, ˇ = 101.256(6)◦
c = 10.744(4) Å, ꢂ = 116.811(6)◦
878.2(6) A3
Volume
3.4. Absorption spectral characteristics of the compounds 5a–g
Z
2
Calculated density
Absorption coefficient
F(0 0 0)
Crystal size
ꢃ range for data collection
Limiting indices
Reflections collected/unique
Completeness to ꢃ = 25.05◦
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2ꢄ(I)]
R indices (all data)
Largest diff. peak and hole
1.525 Mg/m3
The UV–vis spectrum of the compounds 5a–g in ethanol and
dichloromethane are shown in Figs. 3 and 4, respectively, and the
optical characteristics are summarized in Table 3. The results show
that 5a–g display similar absorptions ranging from 300 to 500 nm
and the absorption maximum are about 340 and 460–470 nm
(Table 3).
0.992 mm−1
416
0.21 mm × 0.18 mm × 0.16 mm
2.09–25.05◦
−11 ≤ h ≤ 8, −11 ≤ k ≤ 12, −12 ≤ l ≤ 11
4482/3085 [R(int) = 0.0354]
98.8%
The absorptions in the range of 260–280 nm in ethanol are
attributed to the ␲–␲* transitions arising probably from 3-
aryl-1,2,4-triazole moiety, whereas the longer wavelength region
absorptions between 310 and 380 nm are attributed to the ␲–␲*
transitions of the cyclopentadienyl rings. The absorption bands
between 420 and 500 nm are attributed to metal to ligand charge
transfer (MLCT) transition from Fe to either the non-bonding or the
antibonding orbitals of the cyclopentadienyl rings [35,36].
The data indicated that, when electron-withdrawing sub-
stituent, such as a nitro group, is located on the phenyl ring
at position 3, the absorption peaks assigned to ␲–␲* transitions
of the cyclopentadienyl rings of 5g are at shorter wavelengths
(306 and 305 nm) than those of other compounds in ethanol or
dichloromethane, respectively. But the absorption intensity of 5g
is stronger than that of other compounds. By contrast, the electron-
donating substituent located on the phenyl ring at position 3 could
not obviously affect the absorption spectra of 5.
None
0.8575 and 0.8188
Full-matrix least-squares on F2
3085/0/235
1.050
R1 = 0.0533, wR2 = 0.1372
R1 = 0.0691, wR2 = 0.1497
0.826 and −0.668e Å−3
C4–H4. . .N2 hydrogen bonds and a significant C–H. . .␲ interac-
tion between the phenyl ring hydrogen (C18–H18) and Cg1. The
S1/C12/C11/O1/C1 fragment is almost planar as revealed by the cor-
responding S1–C12–C11–O1 torsion of 1.7(5)◦ and S1–C12–C11–C1
torsion of −177.7(3)◦. The dihedral angles of the S1/C12/C11/O1/C1
plane with the triazole ring and the substituted Cp ring are 83.1(2)◦
and 6.5(2)◦, respectively.
Fig. 3. UV–vis absorption spectra of compounds 5a–g taken in ethanol at 4 × 10−4 M (A) and 4 × 10−5 M (B), respectively.
Fig. 4. UV–vis absorption spectra of compounds 5a–g taken in dichloromethane at 10−3 M (A) and 10−4 M (B), respectively.

W.-Y. Liu et al. / Spectrochimica Acta Part A 76 (2010) 531–536
535
Table 3
The optical characteristics of compounds 5a–g.
Compounds 5a–g
ꢀmax (nm)
εmax (L mol−1 cm−1
)
EtOH
CH2Cl2
EtOH
CH2Cl2
5a
5b
5c
5d
5e
5f
460
460
460
460
460
460
454
335
341
340
339
339
349
306
269
266
266
270
268
262
271
460
468
469
468
464
471
471
341
344
348
344
341
349
305
638
616
589
600
580
633
749
1687
1484
1450
1510
1586
1710
13413
7275
21563
14256
16259
22937
15697
14199
605
710
723
702
664
796
862
1435
1452
1430
1506
1415
1517
13019
5g
Fig. 5. UV-vis absorption spectra of compounds 5a (A) and 5c (B) taken at 10−4 M taken in ethanol, DMF and DCM, respectively.
tra of 5a and 5c, as examples, in three different solvents, EtOH,
CH2Cl2 and DMF, at a concentration of 10−4 M are shown in Fig. 5.
It is noticed that there is obvious difference in maximum absorp-
tion wavelength and hypsochromic shifts is observed as polarity
increasing of solvents.
3.5. Fluorescence spectral characteristics
The maximum excitation wavelengths of 5a–g were 265, 260,
263, 263, 261, 264 and 261 nm respectively, and the emission spec-
tra were taken at the maximum excitation wavelengths in ethanol
at 10−6 M as shown in Fig. 6. It can be found that the emission spec-
tra with maximum emission 566–568 nm for compounds 5a–g are
almost identical except difference in intensity (Table 4).
4. Conclusion
A series of novel ferrocene-containing 1,2,4-triazole derivatives
was synthesized by the reaction of 3-substituted-1H-1,2,4-
triazole-5-thiol with chloroacetyl ferrocene in the presence of
sodium hydride and potassium iodide. The structures of com-
pounds obtained were determined by IR, 1H NMR and HRMS
spectra, typically, the spatial structure of compound 5c was
determined by using X-ray diffraction analysis. Absorption and
fluorescence spectral characteristics of the compounds were inves-
tigated in ethanol and dichloromethane by UV–vis absorption
and emission spectra. The absorption spectra and fluorescence
characteristics were correlated with substituent on triazole
rings.
Fig. 6. Emission spectra of 5a–g in ethanol at 10−6 M and at 265, 260, 263, 263, 261,
264 and 261 nm excitation wavelengths, respectively.
Possible influence of the solvent on the absorption behav-
ior is investigated. Weak solvatochromism is observed in the
absorption bands for all compounds as shown in Table 3. The hyp-
sochromic shifts take place when the solvent is changed from
dichloromethane to ethanol. Furthermore, the absorption spec-
Table 4
Data of fluorescence spectra of compounds 5a–g at 10−6 M in ethanol.
Supplementary materials
Compounds 5a–g
ꢀex (nm)
ꢀem (nm)
Stoke’s shift (nm)
5a
5b
5c
5d
5e
5f
265
260
263
263
261
264
261
566
566
568
567
568
566
566
301
306
305
304
307
302
305
CCDC 749530 contains the supplementary crystallographic
data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data request/cif, by emailing
data request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ,
UK. Fax: +44 1223 336033.
5g

536
W.-Y. Liu et al. / Spectrochimica Acta Part A 76 (2010) 531–536
Acknowledgements
[16] B. Liu, X.C. Zhang, Y.H. Chen, Chem. Commun. 10 (2007) 498–501.
[17] B. Liu, X.C. Zhang, Y.F. Wang, Inorg. Chem. Commun. 10 (2007) 199–
203.
[18] J.A. Key, S. Koh, Q.K. Timerghazin, A. Brown, C.W. Cairo, Dyes Pigm. 82 (2009)
196–203.
[19] H. Sun, Q. Wang, R. Huang, H. Li, Y. Li, J. Organomet. Chem. 655 (2002) 182–185.
[20] H. Yu, L. Shao, J. Fang, J. Organomet. Chem. 692 (2007) 991–996.
[21] M. Zora, M. Görmen, J. Organomet. Chem. 692 (2007) 5026–5032.
[22] A. Caballero, A. Espinosa, A. Tárraga, P. Molina, J. Org. Chem. 72 (2007)
6924–6937.
This study was supported by the Science and Technology Devel-
opmental Project of Shandong Province (2008GG10002034) and
National Natural Science Foundation of China (90813022).
References
[23] F. Zapata, A. Caballero, A. Espinosa, A. Tárraga, P. Molina, J. Org. Chem. 74 (2009)
4787–4796.
[24] B. Delavaux-Nicot, J. Maynadié, D. Lavabre, S. Fery-Forgues, J. Organomet. Chem.
692 (2007) 3351–3362.
[25] R.L. Zhang, Y.S. Wu, Z.L. Wang, W. Xue, H.B. Fu, J.N. Yao, J. Phys. Chem. C 113
(2009) 2594–2602.
[26] S. Fery-Forgues, B. Delavaux-Nicot, J. Photochem. Photobiol. A: Chem. 132
(2000) 137–159.
[27] G. Wells, M. Suggitt, M. Coffils, M.A.H. Baig, P.W. Howard, P.M. Loadman,
J.A. Hartley, T.C. Jenkins, D.E. Thurston, Bioorg. Med. Chem. Lett. 18 (2008)
2147–2151.
[28] S. Chattopadhaya, R. Srinivasan, D.S.Y. Yeo, G.Y.J. Chen, S.Q. Yao, Bioorg. Med.
Chem. 17 (2009) 981–989.
[29] W.Y. Liu, H.Y. Li, B.X. Zhao, D.S. Shin, S. Lian, J.Y. Miao, Carbohydr. Res 344 (2009)
1270–1275.
[30] L.W. Zheng, L.L. Wu, B.X. Zhao, W.L. Dong, J.Y. Miao, Bioorg. Med. Chem. 17
(2009) 1957–1962.
[1] A. Mohammad, K. Harish, A.J. Sadique, Bioorg. Med. Chem. Lett. 17 (2007)
4504–4508.
[2] A. Demirbas, D. Sahin, N. Demirbas, S.A. Karaoglu, Eur. J. Med. Chem. 44 (2009)
2896–2903.
[3] G.R. Jadhav, M.U. Shaikh, R.P. Kale, M.R. Shiradkar, C.H. Gill, Eur. J. Med. Chem.
44 (2009) 2930–2935.
[4] J.P. Marino Jr., P.W. Fisher, G.A. Hofmann, R.B. Kirkpatrick, C.A. Janson, R.K. John-
son, C. Ma, M. Mattern, T.D. Meek, M.D. Ryan, C. Schulz, W.W. Smith, D.G. Tew,
T.A. Tomazek Jr., D.F. Veber, W.C. Xiong, Y. Yamamoto, K. Yamashita, G. Yang,
S.K. Thompson, J. Med. Chem. 50 (2007) 3777–3785.
[5] D.A. Ibrahim, Eur. J. Med. Chem. 44 (2009) 2776–2781.
[6] X. Collin, A. Sauleau, J. Coulon, Bioorg. Med. Chem. Lett. 13 (2003) 2601–2605.
[7] F. Chabchoub, M. Messaâd, H.B. Mansour, L. Chekir-Ghedira, M. Salem, Eur. J.
Med. Chem. 42 (2007) 715–718.
[8] Y.M. Ma, R.H. Liu, X.Y. Gong, Z. Li, Q.C. Huang, H.S. Wang, G. Song, J. Agric. Food
Chem. 54 (2006) 7724–7728.
[9] D.P. Cudworth, V.B. Hegde, M.C.H. Yap, K.A. Guenthenspberger, C.T. Hamilton,
J.T. Pechacek, P.L. Johnson, S.J. Bis, F.E. Tisdell, J.E. Dripps, T.J. Bruce, L.P. Dinten-
fass, J.M. Gifford, L.L. Karr, M.K. Kempe, D.C. McCormick, J.R. Jr Schoonover, J.
Agric. Food Chem. 55 (2007) 7517–7526.
[10] M.H. Klingele, S. Brooker, Coord. Chem. Rev. 241 (2003) 119–132.
[11] F.E. Bradford, L.P. Connor, C.A. Kilner, M.A. Halcrow, Polyhedron 23 (2004)
2141–2151.
[31] B.X. Zhao, L. Zhang, X.S. Zhu, M.S. Wan, J. Zhao, Y. Zhang, S.L. Zhang, J.Y. Miao,
Bioorg. Med. Chem. 16 (2008) 5171–5180.
[32] Y.S. Xie, X.H. Pan, B.X. Zhao, J.T. Liu, D.S. Shin, J.H. Zhang, L.W. Zheng, J. Zhao,
J.Y. Miao, J. Organomet. Chem. 693 (2008) 1367–1374.
[33] L.Y. Harry, J.P. Joseph, J. Med. Chem. 9 (1966) 42–46.
[34] L. Labanauskas, E. Udrenaite, P. Gaidelis, A. Brukstus, Farmaco 59 (2004)
255–259.
[35] P. Barbazán, R. Carballo, U. Abram, G. Pereiras-Gabián, E.M. Vázquez-López,
Polyhedron 25 (2006) 3343–3348.
[36] S. Toma, A. Gaplovsky, I. Pavlik, Monatsh. Chem. 116 (1985) 479–486.
[12] L. Demange, D. Boeglin, A. Moulin, D. Mousseaux, J. Ryan, G. Bergé, D. Gagne,
A. Heitz, D. Perrissoud, V. Locatelli, A. Torsello, J.C. Galleyrand, J.A. Fehrentz, J.
Martinez, J. Med. Chem. 50 (2007) 1939–1957.
[13] Z. Chen, X. Li, F. Liang, J. Solid State Chem. 181 (2008) 2078–2086.
[14] B. Liu, L. Xu, G.C. Guo, J.S. Huang, J. Mol. Struct. 825 (2006) 79–86.
[15] S.W. Liang, M.X. Li, M. Shao, X. He, J. Mol. Struct. 875 (2008) 17–21.