S. El-din H. Etaiw and A. H. Werida
H, 4; N, 9.3%. Anal. calcd for [(BQ)0.067(2-HBQ)0.933 (n-Bu3Sn)3.5 Fe
•
(
CN)6] H2O 5 (C54 H100.5 N6 Sn3.5 Fe O4): C, 48.0; H, 7.5; N, 6.2%.
n
Found: C, 47.7; H, 7.2; N, 6.3%. Anal. calcd for [(BQ)0.1(2-HBQ)0.90
•
(
Ph3Sn)4 Fe (CN)6] 3H2O 6 (C48 H70 N6 Sn4 Fe O6): C, 56.8; H, 3.9; N,
n
4
.7%. Found: C, 56.4; H, 3.9; N, 4.8%.
Instruments
The IR and UV–vis spectra were recorded on Perkin Elmer SP
1
430 and Shimadzu 3101 PC spectrophotometers, respectively.
Elemental analyses were carried out on a Perkin Elmer 2400
automatic elemental analyzer. The X-ray powder diffraction
patterns were recorded using a Philips PW-1729 (Cux –Kα radiation
using Ni filter). The simulated X-ray diffraction patterns were
obtainedusingaMercury2.2program. Themagneticsusceptibility
was determined with Johnson–Matthey susceptometer. HPLC
experiments were carried out on HPLC, Waters 2690 series. HPLC
experiments for PNP were conducted using an X-bridge C18
column (5 µm particle size, 150 × 4.6 mm) with a flow rate of
−
1
1
.5 ml min at room temperature. The mobile phases used were
acetonitrile and methanol–water (1 : 1, v/v). HPLC experiments for
resorcinol were carried out using a reverse-phase C18 Atlantis
−
1
column (250 × 4.6 mm) with a flow rate of 1.5 ml min
at
room temperature. The mobile phase used consisted of 10 mM
ammonium formate, with pH adjusted to 3.0 using formic acid.
The solid materials were heated in methanol using ultrasonic
bath. A 20 µL volume of each solution was filtered off and then
injected into the column. The concentrations of resorcinol and
p-nitrophenol were determined by HPLC.
Figure 1. Comparison of the simulated and experimental X-ray diffrac-
tograms of the host supramolecular coordination polymers I–III.
Results and Discussion
R3Sn units owing to their axial anchoring to two cyanide N
atoms.[
14]
The powder X-ray diffractions of I–III were compared with
simulated X-ray diffractions based on data resulting from the
The electronic absorption spectra of I–III in Nujol mull matrices
reveal mainly three absorption bands in the region 220–432 nm.
The first band at 220 nm is due to π –π transitions from iron to
[
10–12]
structure analyses of single crystals of I–III
(Fig. 1). The
∗
experimental and simulated X-ray diffraction diffractograms look
very similar, suggesting immediately that the final powdered
bulk samples of I–III should be structurally closely related to
the crystalline forms. The common feature of these SCPs is
the polymeric nonlinear [Fe–C N–Sn–N C–Fe]n chains which
intersect to build up the 3D-network structure. The alkyl or phenyl
groups are disordered over three positions with their trigonal
arrangement preserved. The difference between the structures
of the methyl-, n-butyl- and phenyl-tin SCPs arises from the
constraints imposed by packing the ligands with the framework
definedbytheFe–CN–Snbonds.Thepresenceofremarkablewide
channels whose walls are internally coated by constituents of the
lipophilic R3Sn groups allows encapsulation of resorcinol or PNP,
which undergoes in situ oxidation forming new HGSCPs.[10–12]
The IR spectra of I–III display a strong intensity band at
the cyanide ligand (M → L). The composite band at 310–330 nm
2
2
[15]
corresponds to ligand field (d–d) transitions ( A2g → T1g).
∗
The low energy band at 419–430 nm corresponds to π –π
III
3−
transitions of the [Fe (CN)6] building blocks. The SCPs I–III
exhibit paramagnetic behavior with magnetic values, µeff equal to
2.036, 2.32 and 2.291 BM, respectively, supporting the presence of
III
3−
[Fe (CN)6] building blocks.
Spectral characterstics of the HGSCPs 1–6
Resorcinol and PNP undergo in situ oxidation within the channels
of the SCPs I–III while in some cases the SCPs exhibit partial
reduction. The IR spectra of 1–3 reveal a broad band at 3420,
−
1
3423 and 3410 cm , respectively, corresponding to νH2O. The
−
1
2
145, 2133 and 2141 cm , respectively, due to νC N. These
IR spectrum of resorcinol exhibits two strong bands at 3257
−
1
values are much higher than those of the genuine salts of the
and 3208 cm due to stretching vibrations of the two hydroxyl
III
3−
−1
corresponding [Fe (CN)6] anions (νC N = 2116 cm ). This
increase in the vibration wavenumbers of the cyanide bond
suggests the presence of a nonlinear chain with anticipated
bridges [Fe–C N–Sn–N C–Fe]. The νFe–C band of I–III at
groups. On the other hand, the IR spectra of 1–3 reveal a broad
−
1
band around 3250 cm due to νOH of the oxidation product. γCH
−
1
vibrations of resorcinol appear at 843 and 680 cm due to the
isolated CH bond and the three adjacent CH bonds, respectively,
while they appear in the IR spectra of 1–3 at 860 and 790 cm
−
1
−1
4
07, 403 and 411 cm , respectively, reflects the presence of the
octahedral [Fe (CN)6] building blocks.
vibrations at 547, 519 and 582 cm for I–III, respectively, reflect
the presence of Sn–C bonds, while the absence of the symmetric
νSn–C band advocates the exclusive presence of trigonal planar
III
3−
[13]
The IR-active νSn–C
due to the isolated CH bond and the two adjacent CH bonds,
respectively. These IR bands indicate that resorcinol is oxidized to
the corresponding 1,2,4-trihydroxy benzene (THB). This opinion
wasfurthersupportedbythepresenceofthebandsofthebenzene
−
1
wileyonlinelibrary.com/journal/aoc
Copyright ꢀc 2010 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2010, 24, 805–808