Synthesis, spectroscopy and flower-like morphology of ferrocene schiff base

Article abstract of DOI:10.1080/15533170903129877

Novel ferrocene Schiff bases bearing phenylferrocene was synthesized by facile methods. The compound prepared was characterized by spectroscopic methods (IR, UV-visible, 1H NMR, mass spectrometry) and elemental analysis. It was found for the first time th

Full text of DOI:10.1080/15533170903129877

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 39:416–418, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533170903129877
Synthesis, Spectroscopy and Flower-like Morphology
of Ferrocene Schiff Base
Yu-Mei Zhang, Peng Liu, and Hong-Li Zhang
College of Sciences, Hebei University of Science & Technology, Shijiazhuang, China
attributed to aromatic νC H. A sharp band around 1103.9 and
996.6 cm−1 due to ferrocene is observed in the spectra of the
Novel ferrocene Schiff bases bearing phenylferrocene was syn-
thesized by facile methods. The compound prepared was charac-
terized by spectroscopic methods (IR, UV–visible, 1H NMR, mass
spectrometry) and elemental analysis. It was found for the first
time that that the compound can self-assemble 3D flower-like hier-
archical spheres composed of small nanosheets by precipitate from
CHCl3 solution drop-cast on Si wafer.
compound. An Cp νC H stretching vibration is also seen around
486.1 cm−1 and 509.9 cm−1
.
1
All the characteristic signals are observed in the H NMR
spectra of the synthesized schiff bases. The hydrogen atoms of
the unsubstituted cyclopentadienyl ring moiety appear as a sharp
singlet, in the 4.027 ppm for five hydrogens and the substituted
one at 4.350–4.355 ppm for two hydrogens and at 4.671–4.677
ppm for the other two hydrogens. The hydrogen atom of the
Imine function shows a sharp singlet at 8.621 ppm. Signals at
7.22-8.34 ppm belonged to phenyl protons.
Keywords ferrocene, flower-like, morphology, schiff base, synthesis
INTRODUCTION
UV–visible studies were carried out in trichloromethane
(Figure 1). The absorption spectra of compound 2 in di-
lute CHCl3 solution (10−6 M) exhibited three major bands
with absorption λmax at about 282,370, and 483 nm. com-
pared with the 4-ferrocenylaniline 1, the peak at 251 nm red-
shifted about 31 nm to 282 nm, while the absorption band
at 290 nm also red-shifted 80 nm to 370 nm. Such absorp-
tion results indicated the conjugated chain growth of compound
2.
Figure 2 illustrates the SEM image of 2 directly precipitated
from CHCl3 solution. The flower- like structures was achieved
from drop-casting the CHCl3 solution of compound 2 on the sili-
con wafer. Compound 2 showed 3D molecular assembly flower-
like morphology. The nanostructures of compound 2 from so-
lution showed its potential applications in various integrated
optoelectronic devices via solution process.
One of the areas of organic chemistry that has un-
dergone major developments in recent years is that con-
cerning ferrocene schiff base compounds. Ferrocene-based
schiff bases have been employed in various fields, such as
semiconductors,[1,2] biosensors,[3−5] asymmetric catalysis,[6,7]
and nonlinear optics.[8,9] In addition Schiff bases can also ex-
hibit biological activities including antifungal,[10] antiviral[11]
and anticancer activities.[12] In this manuscript, we report the
preparation and characterization (IR, 1H NMR, UV–visible and
elemental analyses) of ferrocene Schiff bases 2 and first report
its morphology, the tunable nanostructures of 2 from solution
showed its potential applications in various integrated optoelec-
tronic devices via solution process.[13,14] Application of this
compound is under way (Scheme 1).
RESULTS AND DISCUSSION
The elemental analysis of the product is in good agreement
with the calculated values. The I.R spectra of the product show
all the characteristic peaks. A broad absorption band at 1615 EXPERIMENTAL
cm−1 is assigned to νC N. The bands around 3102 cm−1 can be
General
Commercially available chemicals were used without fur-
ther purification unless stated otherwise. 1H NMR spectra were
recorded on a Varian Mercury 300 (300 MHz) spectrometer in
CDCl3 with TMS as the reference. IR spectra were obtained
using KBr pellets on a Nicolet 179SX FT-IR spectrometer. El-
emental analysis of the compound was performed on an Ele-
mentar Vario EL (Germany) instrument. UV-vis spectra were
recorded on Perkin Elmer Lambda 35 UV-vis spectra.
Received 23 March 2009; accepted 28 April 2009.
This work was financially supported by the foundmental research
fund of Hebei University of Science & Technology (XL200823) and
discipline improvement fund of Hebei University of Science & Tech-
nology.
Address correspondence to Yu-Mei Zhang, College of Sciences,
Hebei University of Science & Technology, Shijiazhuang, 050018,
China. E-mail: zhangym.jy@gmail.com
416

MORPHOLOGY OF FERROCENE SCHIFF BASE
417
Synthesis of N-(4-nitrobenzylidene)-4-ferrocenylaniline
To a solution of 4-ferrocenylaniline (277 mg, 1.0 mmol)
in absolute ethanol (20 ml) stirred 15 min and then added 4-
Nitrobenzaldehyde (164 mg, 1.1 mmol). The reaction mixture
was refluxed for 4 h. After cooling the product was collected by
filtration, washed with cold absolute ethanol, recrystallized from
absolute ethanol and characterized by spectroscopic methods
and elemental analyses. Yield: 352 mg (86.1%).
SCH. 1. The synthesis of compound 2.
IR (KBr, υmax, cm−1): The IR spectrum indicated the pres-
ence of the unsubstituted cyclopentadienyl ring (1103.9 and
996.6 cm−1), 1022.0 ∼ 1147.6 cm−1 (single substituted cy-
clopentadienyl), 486.1 cm−1 and 509.9 cm−1 (νFe−C), 1615
1
cm−1(N CH); H NMR (300 MHz, CDCl3, TMS, δ , ppm):
8.621(s, 1H, CH N), 8.341 (d, 2H, C6H4, J = 8.7), 8.095 (d,
2H, C6H4, J = 8.7), 7.543 (d, 2H, C6H4, J = 8.1), 7.256 (d,
2H, C6H4, J = 8.4), 4.355 (d, 2H,C5H4, J = 1.5), 4.677 (d,
2H,C5H4, J = 1.8) ,4.027 (s, 5H, Fc-unsubstituted ring). Anal.
calcd for C23H18N2O2Fe: C, 67.34; H, 4.42. Found: C, 66.48; H,
4.40%. UV–visible [λ max (CHCl3), nm]: 282, 370, and 483 nm.
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FIG. 2. Morphology of self-assembled compound 2: (A) Large-area SEM
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1 µm.)

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