Ansa-ferrocene-incorporated calixpyrroles and calixphyrins: Syntheses and spectral/structural characterization

Article abstract of DOI:10.1021/om300004m

The syntheses and spectral/structural characterization of ansa-ferrocene-incorporated normal calixphyrins and core-modified calixpyrroles and calixphyrins are reported. Acid-promoted dehydrative condensation of 1,1′-bis(dimethylpyrrolylmethyl)ferrocene and 2,5- bis(dimethylhydroxymethyl)thiophene/furan yielded ansa-ferrocene-based core-modified calixpyrroles, while acid-catalyzed dehydrative condensation of 1,1′-bis(diphenylpyrrolylmethyl)ferrocene with the aryl aldehydes and 2,5-bis(phenylhydroxymethyl)thiophene followed by DDQ oxidation resulted in the formation of ansa-ferrocene-appended normal and core-modified calixphyrins, respectively. The newly synthesized macrocycles were characterized by FAB-MS, NMR, and UV-vis spectral analyses and finally confirmed by single-crystal X-ray structural analysis. All these studies clearly revealed the introduction of ferrocene in the main framework of the corresponding macrocycles in an ansa-type way. The core-modified calixpyrroles adopt a 1,3-alternate conformation, while the corresponding calixphyrins maintained partial planarity along the tripyrrin plane due to the presence of meso sp² carbon and generated curved staircase conformation. In addition to the intramolecular hydrogen-bonding interactions, calixphyrins generate self-assembled dimers, one- and two-dimensional supramolecular assemblies through intermolecular hydrogen bonding in the solid state.

Full text of DOI:10.1021/om300004m

Article
pubs.acs.org/Organometallics
ansa-Ferrocene-Incorporated Calixpyrroles and Calixphyrins:
Syntheses and Spectral/Structural Characterization
S. Ramakrishnan,† K. S. Anju,† Ajesh P. Thomas,‡ K. C. Gowri Sreedevi,† P. S. Salini,†
M. G. Derry Holaday,† Eringathodi Suresh,§ and A. Srinivasan*,‡
†Photosciences and Photonics Section, Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science
and Technology (NIIST−CSIR), Thiruvananthapuram−695019, Kerala, India
‡School of Chemical Sciences, National Institute of Science Education and Research (NISER), Bhubaneswar−751005, Odisha, India
§Analytical Science Discipline, Central Salt and Marine Chemical Research Institute (CSMCRI-CSIR), G. B. Marg,
Bhavnagar−364002, Gujarat, India
S
* Supporting Information
ABSTRACT: The syntheses and spectral/structural charac-
terization of ansa-ferrocene-incorporated normal calixphyrins
and core-modified calixpyrroles and calixphyrins are reported.
Acid-promoted dehydrative condensation of 1,1′-bis-
(dimethylpyrrolylmethyl)ferrocene and 2,5-bis-
(dimethylhydroxymethyl)thiophene/furan yielded ansa-ferro-
cene-based core-modified calixpyrroles, while acid-catalyzed
dehydrative condensation of 1,1′-bis(diphenylpyrrolylmethyl)ferrocene with the aryl aldehydes and 2,5-bis-
(phenylhydroxymethyl)thiophene followed by DDQ oxidation resulted in the formation of ansa-ferrocene-appended normal
and core-modified calixphyrins, respectively. The newly synthesized macrocycles were characterized by FAB-MS, NMR, and UV−
vis spectral analyses and finally confirmed by single-crystal X-ray structural analysis. All these studies clearly revealed the
introduction of ferrocene in the main framework of the corresponding macrocycles in an ansa-type way. The core-modified
calixpyrroles adopt a 1,3-alternate conformation, while the corresponding calixphyrins maintained partial planarity along the
tripyrrin plane due to the presence of meso sp2 carbon and generated curved staircase conformation. In addition to the
intramolecular hydrogen-bonding interactions, calixphyrins generate self-assembled dimers, one- and two-dimensional
supramolecular assemblies through intermolecular hydrogen bonding in the solid state.
isoporphyrins,19 5,10- or 5,15-dihydroporphyrins,18f,20 porpho-
INTRODUCTION
Porphyrinogens, the meso-reduced derivatives of porphyrins,
■
mono,21 and dimethenes,20,21a,b,22 higher order calix[n]phyrins
(n > 4),1d,23 three-dimensional calixphyrin,24 hybrid calixphyr-
ins,22e−i,25 and N-confused calixphyrins26 are known in the
literature.
have significant roles in both natural and artificial systems.1
Their rich anion binding abilities, metal complexation character,
unique redox properties, molecular recognition behavior, etc.,
make them versatile molecules.1 Introduction of dialkyl or
diaryl or alkyl-aryl substituents onto the meso sp3-hybridized
carbon prevents the oxidative aromatization of porphyrinogens
to porphyrins. However, the important difference lies in the
coordination behavior of porphyrins and porphyrinogens; the
former are dianionic ligands, whereas the latter are tetra-anionic
ligands toward metal complexation.1 There are two types of
porphyrinogens: calixpyrroles,1e where all the meso carbons are
sp3 hybridized, and calixphyrins,1d,f,g where at least one of the
meso carbons is sp2 hybridized. A series of calixpyrroles, namely,
calix[5]pyrrole,2,4 calix[6]pyrrole,3 hexadecafluorocalix[8]-
pyrrole,4 calixbipyrrole,5 strapped calixpyrrole,6 calixpyrrole
dimer,7 N-confused calix[4]pyrrole,8 cryptand-like calixpyr-
role,9 aza tri- and tetrapyrrolic macrocycles,10 calix[1]-
pyrene[3]pyrrole,11 expanded calix[n]pyrrole,12 and core-
modified calixpyrroles having benzene,13 carbazole,14 furan,5b,15
phosphole,16 and thiophene5b,15a,c,e,17 analogues, are reported.
Many examples of calixphyrin derivatives, such as phlorins,18
On the other hand, the metallocenes have been used as
electrochemically active substituents, which are covalently or
noncovalently linked to the receptor moieties such as
porphyrinogens and single- or multi-porphyrin assemblies. In
1998, Sessler and co-workers reported an ansa-ferrocene-
bridged macrocycle (A) (Chart 1) in which the ferrocene
subunit is covalently bonded with two pyrrole units strapped
with an amide-linked oligoether, which acts as a redox-based
sensor for F− and H2PO4 anions.27 In 2001, another group
−
reported a meso ferrocenyl calix[4]pyrrole (B) (Chart 1) where
the ferrocene is substituted at one of the meso positions of the
calixpyrrole framework, which has been tested as an electro-
chemical sensor for various anions.28f Recently, Bucher and co-
workers reported meso ferrocenyl calix[4]phyrin (C) (Chart 1),
which contains only one sp2-hybridized meso carbon with a
Received: January 3, 2012
Published: May 24, 2012
© 2012 American Chemical Society
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Article
Chart 1
Scheme 1. Syntheses of 6−11
ferrocene unit.28g In addition to these, metallocene-appended
porphyrins28a−e have also been synthesized, which were found
suitable for multiple electron transfer reactions and molecular
electronic devices.27,28 However, incorporation of metallocenes
into the integral part of the fully/partially conjugated
macrocycles is rare.27,29
trifluoroacetic acid-catalyzed condensation reaction of 129a with
3 and 430 in CH2Cl2 followed by column chromatographic
purification, resulting in stable yellow-colored macrocycles 6
and 7 in 28% and 27% yield, respectively, whereas Scheme 1b
and c involved similar acid-catalyzed condensation of 2 with
equimolar quantity of aryl aldehydes and 531 followed by
oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ), resulting in the formation of stable red-colored
macrocycles 8−10 in 17−19% and 11 in 4% yield.29e However,
no higher analogues could be isolated upon purification of the
crude mixture. All the macrocycles are soluble in almost all the
organic solvents such as CH2Cl2, CHCl3, and CH3CN.
Recently, we have demonstrated the syntheses and spectral/
structural characterization of normal calix[1]metallocenyl[2]-
pyrrole (D)29a (Chart 1), where the pyrrole units in the main
framework adopt a 1,2-alternate conformation in the solid state,
proving that the macrocycle retains the calix[4]pyrrole
behavior.1e Subsequently, Latos-Grazyn
́
ski and co-workers
̇
reported ansa-metallocene macrocycles in which the metal-
locene is connected with a conjugated oligopyrrole unit, such as
dipyrrin (F) or heterotripyrrin (G), where the helical
conformations and dynamic behavior of these macrocycles
have been explored by NMR spectroscopy.29b Very recently,
the same group also reported the synthesis and characterization
of ferrocenothiaporphyrin and dihydroferrocenothiaporphyrin,
which possessed macrocyclic antiaromaticity and aromaticity
and provided evidence for direct transmission of π-electron
conjugation across a d-electron metallocene.29c In addition to
the metallocene-appended dipyrrin macrocycle (F)29b (Chart
Spectral Analyses. The FAB mass spectral analyses of all
the new macrocycles 6−11 show the molecular ion signals at
564.87, 548.60, 748.22, 758.80, 834.08, and 904.68, respec-
1
tively, which proves the exact composition. The H NMR
spectra of 6−11 (Table 1) were recorded in CDCl3 at room
1) reported by Latos-Grazynski et al., very recently, we
́
̇
Table 1. NMR Spectral Data of 6−11
synthesized expanded calix[n]metallocenyl[m]phyrins,29d
where the macrocycles bear analogy to both calixpyrrole and
porphyrin macrocycles, generating a two-dimensional supra-
molecular assembly in the solid state, and the role of aryl versus
alkyl in the meso position of 1,1′-ferrocenyldipyrromethane was
also highlighted to explain the formation of expanded
macrocycles. In all these macrocycles, metallocene units are
incorporated into the backbone of the respective macrocyclic
framework. Introduction of one more heterocyclic rings such as
thiophene/furan in the above-mentioned metallocene-ap-
pended porphyrinogen framework leads to novel expanded
macrocycles having unusual spectral properties due to altered
electronic structure and core sizes. Herein, we wish to report
the syntheses and spectral/structural characterization of ansa-
ferrocene-incorporated core-modified calixpyrrole (E) and
normal (F) and core-modified calixphyrin (G)29b (Chart 1).
NH
β-pyrrolyl, β-athienyl/bfuranyl
ferrocenyl CH
(ppm)
compound (ppm)
CH (ppm)
a
6
7
8
8.21
8.36
5.98−5.96, 5.87−5.85, 6.78
5.96−5.95, 6.05
6.62−6.61, 5.81−5.8
6.48−6.47, 5.87−5.85
5.98−5.97, 5.69−5.67
4.19−3.97, 3.35
4.02−3.82
4.59, 3.94, 3.86,
2.89
b
16.26
9
16.18
16.41
4.57, 3.97, 3.86,
2.93
10
11
4.76, 4.01, 3.90,
3.02
a
6.78−6.77, 6.64−6.63, 6.74
5.86, 4.14, 3.66,
3.01
temperature (Figure 1), where the NH protons of the
macrocycles 6 and 7 appeared as a broad singlet with a
chemical shift value of 8.21 and 8.36 ppm, respectively.
Incorporation of one more heterocyclic ring in the macrocycles
(6 and 7) leads to 0.33 and 0.48 ppm downfield shifts of the
NH protons as compared to normal calix[1]ferrocenyl[2]-
pyrrole (D),29a suggesting expansion in the macrocyclic
framework.
RESULTS AND DISCUSSION
■
Syntheses. The syntheses of ansa-ferrocene-incorporated
core-modified calixpyrroles and normal and core-modified
calixphyrins are summarized in Scheme 1. Scheme 1a utilizes
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Ultraviolet−Visible Spectral Analyses. The UV−vis
spectral characteristics of the macrocycles 8−11 (Table 2)
Table 2. Absorption Spectral Data of 8−11
compound in
CHCl3
λabs (ε × 105) [nm (M−1 cm−1)]
8
468.5 (0.33)
467.4 (0.38)
9
10
332 (0.497), 348.5 (0.71), 366.5 (0.957), 386 (0.94),
474.5 (1.9)
11
494.8 (0.38), 520 (0.41)
turned out to be generally comparable to those of calix[n]-
phyrin-type macrocycles.29d In the electronic spectral analysis
of the macrocycles 8−11 in CHCl3, broad absorption bands,
which originated due to π → π* transitions in the dipyrrin
moiety, were observed between 400 and 575 nm with molar
extinction coefficient values ranging from 33 000 to 1 90 000
M−1cm−1. Absorption spectra of 11 were red-shifted by 20−25
nm compared with 8−10, which proves the extended π-
conjugation in 11 (Figure 2). The absorption bands
1
Figure 1. H NMR spectra of (a) 6, (b) 9, and (c) 11 in CDCl3. (i)
Ferrocenyl CH, (ii) pyrrolic-β-CH, (iii) thienyl-β-CH, (iv) NH.
*Solvent peak, and the remaining are phenyl protons.
The NH protons of the macrocycles 8−10 appeared as a
broad singlet at the high deshielded region with a chemical shift
value of 16.26, 16.18, and 16.41 ppm, respectively. The drastic
shift of NH is mainly due to delocalization of the lone pair of
electrons on the pyrrolyl amine nitrogen atom of the
macrocycles and also the presence of an intramolecular
hydrogen-bonding interaction between amine NH and imine
N in the dipyrrin moiety. All the NH protons of 6−10 were
confirmed by D2O exchange experiments.
Figure 2. UV−vis absorption spectra of 10 (dotted line) and 11 (solid
line) in CHCl3.
The thienyl-β-CH protons of 6 and 11 appeared as a singlet
at 6.78 and 6.74 ppm, whereas furanyl-β-CH protons of 7
appeared at 6.05 ppm. Due to the heavier heteroatom effect,
the thienyl-β-CH protons in 6 are 0.73 ppm deshielded when
compared with the furanyl-β-CH protons of 7. The pyrrolic-β-
CH protons of all the macrocycles 6−11 resonated between 6.8
and 5.6 ppm. Due to partial delocalization of electron density,
the pyrrolic-β-CH protons of 11 are deshielded with a shift
difference of 0.80 ppm when compared with 6. The
disappearance of the pyrrolic-α-CH proton peaks of 1 at 6.48
ppm and 229a at 6.69 ppm suggests the formation of
macrocycles 6−11.
Finally, the ferrocenyl CH protons of 6 and 7 split into two
different sets to give a multiplet resonating at 4.19−3.80 ppm
and a singlet at 3.35 ppm. However, in 11, out of eight protons,
two protons appeared as a singlet at the deshielded region with
a shift value of 5.86 ppm, whereas the remaining six protons
resonated between 4.14 and 3.01 ppm. In the case of 8−10, the
respective protons resonated as a set of four singlets between
4.76 and 2.89 ppm. This suggests that two cyclopentadienyl
rings in 8−11 are in restricted rotation at room temperature
due to the presence of four phenyl rings on two sp3-hybridized
meso carbons which are directly attached to the 1 and 1′
position of ferrocene.
corresponding to π → π* transitions of the anthracene moiety
were observed at the lower wavelength absorption region
between 332 and 386 nm with molar extinction coefficient
values ranging from 96 000 to 49 000 M−1 cm−1, respectively
for 10 (Figure 2). All the macrocycles are nonfluorescent in
their free base form.
Single-Crystal X-ray Structural Analyses. The final
confirmation of the macrocycles 6 and 8−11 comes from
single-crystal X-ray structural analyses (Table 3), which are
shown in Figures 3, 4, and 5. Good-quality X-ray crystals of 6
and 8−11 were grown by slow diffusion of heptanes into their
CHCl3 solutions. As predicted from the above observations,
one ferrocene, two pyrrole units, and two meso sp3-hybridized
carbons each containing two methyl groups in 6 and two
phenyl groups in 8−11 are present, where the α position of the
pyrrole groups is connected to the 1 and 1′ position of
ferrocene via sp3-hybridized meso carbon bridges. On the other
hand, the α′ position of the pyrrole units is connected with
thiophene through two sp3 meso carbons containing four
methyl groups in 6 and two sp2 meso-carbons containing two
phenyl groups in 11 to form the core-modified expanded
calixpyrrole and calixphyrin, whereas with various aryl moieties
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Table 3. Crystal Data, Data Collection and Refinement Parameters for Compounds 6 and 8−11
parameter
6
8
9
10
C59H41FeN2
11
empirical formula
Mw
C34H40FeN2S
564.59
C52H40FeN2
C52H37FeN3
C63H47Cl3FeN2S
1026.29
748.71
759.70
833.79
100(2)
0.71073
triclinic
T [K]
293(2)
100(2)
100(2)
100(2)
λ [Å]
0.71073
0.71073
0.71073
0.71073
cryst syst
space group
a [Å]
monoclinic
Cc
monoclinic
P21/n
monoclinic
P21/c
triclinic
P1
̅
P1
̅
10.8142(6)
22.5198(14)
13.0638(7)
90.00
16.4365(15)
9.8425(9)
23.296(2)
90.00
18.3257(17)
15.9064(15)
12.7614(11)
90.00
10.7256(16)
10.8554(14)
13.2066(17)
17.776(2)
b [Å]
13.681(2)
c [Å]
17.613(2)
α [deg]
β [deg]
γ [deg]
V [Å3]
112.668(2)
93.344(3)
99.425(2)
113.378(3)
90.00
91.443(2)
90.00
93.401(2)
90.00
101.517(2)
94.053(2)
105.922(2)
2253.8(5)
2920.3(3)
4, 1.284
3767.5(6)
4, 1.320
3713.3(6)
4, 1.359
2449.3(5)
Z, ρcalcd [Mg m−3
]
2, 1.229
2, 1.389
μ(Mo Kα) [mm−1
]
0.613
0.441
0.449
0.376
0.559
cryst size [mm]
0.30 × 0.20 × 0.20
0.42 × 0.32 × 0.19
1.50 to 28.26
0.40 × 0.24 × 0.14
1.70 to 25.00
0.35 × 0.20 × 0.15
1.65 to 25.00
0.32 × 0.21 × 0.11
1.19 to 28.27
θ range for data collection 1.81 to 30.99
[deg]
limiting indices
−15 ≤ h ≤ 15,
−32 ≤ k ≤ 32,
−18 ≤ l ≤ 17
37 453
−21 ≤ h ≤ 21,
−12 ≤ k ≤ 13,
−30 ≤ l ≤ 30
31 454
−21 ≤ h ≤ 16,
−18 ≤ k ≤ 18,
−11 ≤ l ≤ 15
18 392
−12 ≤ h ≤ 12,
−16 ≤ k ≤ 15,
−20 ≤ l ≤ 20
16 106
−14 ≤ h ≤ 14,
−17 ≤ k ≤ 17,
−23 ≤ l ≤ 23
21 017
reflns collected
indep reflns [R(int)]
refinement method
8676 [0.0376]
8910 [0.0613]
6524 [0.0727]
7866 [0.0518]
11 082 [0.0232]
full-matrix least-squares
full-matrix least-squares
full-matrix least-squares
full-matrix least-squares
full-matrix least-squares
on F2
on F2
on F2
on F2
on F2
data/restraints/params
goodness-of-fit on F2
8676/4/359
1.007
8910/0/501
1.129
6524/0/505
1.131
7866/0/560
1.043
11 082/0/631
1.119
final R indices [I > 2σ(I)] R1 = 0.0320,
R1 = 0.0642,
wR2 = 0.1305
R1 = 0.0841,
wR2 = 0.1383
0.588 and −0.545
R1 = 0.0694,
wR2 = 0.1286
R1 = 0.0942,
wR2 = 0.1379
0.612 and −0.447
R1 = 0.0715,
wR2 = 0.1830
R1 = 0.0960,
wR2 = 0.1944
0.700 and −0.604
R1 = 0.0608,
wR2 = 0.1450
R1 = 0.0673,
wR2 = 0.1491
0.796 and −0.519
wR2 = 0.0849
R indices (all data)
largest Δρ [e Å−3
R1 = 0.0400,
wR2 = 0.0936
0.335 and −0.214
]
cloud; (b) the ferrocenyl C−H moiety interacts with the
phenylic π-cloud; and (c) one of the phenylic C−H from the
meso sp3 carbon interacts with the ferrocenyl π-cloud. The
distances and angles are (a) C40−H40···thiophene (π): 2.74 Å,
156°; (b) C4−H4···phenyl (π): 2.99 Å, 130°; and (c) C35−
H35···ferrocenyl (π): 2.96 Å, 143°, respectively. These self-
assembled dimers interact with each other to form three one-
dimensional arrays (see the Supporting Information), which
further combine to generate a two-dimensional supramolecular
assembly in the solid state as shown in Figure 4c.
The macrocycles 8−10 are isostructural with earlier reported
calix[1]metallocenyl[2]phyrins.29d As revealed from the NMR
analysis of 8−10, the amine and imine units in the dipyrrin
moiety form intramolecular hydrogen-bonding interactions
with bond distances and angles for N2−H2C···N1 in 8, N1−
H1C···N2 in 9, and N1−H1C···N2 in 10 of 1.89 Å, 137°; 2.03
Å, 122°; and 2.00 Å, 129°, respectively. The meso-p-tolyl in 8,
meso-p-cyanophenyl in 9, and meso-9-anthryl in 10 are deviated
from the mean dipyrrin plane with deviations of 37.76°, 50.52°,
and 63.14°, respectively. In addition to intramolecular hydro-
gen-bonding interactions, 8 also generates a self-assembled
dimer and one-dimensional array (Figure 5g) through the
intermolecular hydrogen-bonding interactions. One of the
meso-phenyl C−H units (C51−H51) in 8 interacts with the
pyrrolic π-cloud to generate a self-assembled dimer, while the
meso-tolyl C−H unit (C40−H40C) interacts with the meso-
phenylic π-cloud to form a one-dimensional array, where the
Figure 3. Single-crystal X-ray structure of 6. (a) Top view, (b) side
view. meso-Methyl groups are omitted for clarity.
via a sp2-hybridized meso carbon in 8−10 to generate normal
calixphyrins.
The crystal analysis of 6 shows that both the pyrrole units are
arranged in a head-on manner and adopt a 1,3-alternate
conformation (Figure 3a) in the solid state, as in the case of the
parent calix[4]pyrrole unit,1e where the distance between two
pyrrolic nitrogens is 5.61 Å.
As observed in the NMR spectral analyses of 11, the crystal
structure also reveals the partial planarity along the tripyrrin
plane and adopts a curved staircase like conformation, as shown
in Figure 4b. The close observation of 11 shows the formation
of three self-assembled dimers through the intermolecular
hydrogen-bonding interactions: (a) the phenyl C−H group that
is present in the meso sp2 carbon interacts with the thienyl π-
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macrocycles have been elucidated by single-crystal X-ray
studies. From the structural analyses, ansa-ferrocene-based
calix[1]thienyl[2]pyrrole adopts a 1,3-alternate conformation
and retains the parent calix[4]pyrrole behavior, whereas ansa-
ferrocene-based calix[2]phyrins and calix[1]thienyl[2]phyrin
are partially planar systems and generate curved staircase
conformations. In addition to the intramolecular hydrogen-
bonding interactions in the dipyrrin moieties, the calixphyrins
reported here also generate a series of supramolecular
assemblies through intermolecular hydrogen bonding. Due to
the presence of ferrocene in an ansa-type way, these
macrocycles are highly rigid in the solid state. Efforts are
currently under way to explore the receptor properties of these
macrocycles in our lab.
EXPERIMENTAL SECTION
■
General Procedures. The starting materials were purchased from
S. D. Fine Chemicals and Aldrich Chemical Co. and used without
further purification unless otherwise stated. All the solvents were
purified and distilled before use. Petroleum ether used was the fraction
with bp 60−80 °C. NMR spectra were recorded with a Bruker 300 or
500 MHz spectrometer with CDCl3 as solvent. Chemical shifts are
expressed in parts per million (ppm) relative to TMS. FAB mass
spectra were obtained on a JEOL SX-120/DA6000 spectrometer using
argon (6 kV, 10 mA) as the FAB gas. UV/vis spectra were recorded on
a Perkin-Elmer−Lambda 25 UV−visible spectrophotometer. TLC
analyses were carried out on aluminum sheets coated with silica gel 60
(Merck 5554). Column chromatography was performed on silica gel
100−200 mesh. Cyclic voltammetric studies were done on a CHI
model 620B CV apparatus (CH instruments, Inc.) interfaced to a
computer. A three-electrode system consisting of a platinum working
electrode and commercially available saturated calomel electrodes, a
reference electrode, and a platinum mesh counter electrode was used.
The reference electrode was separated from the bulk of the solution by
a fritted glass bridge filled with the solvent/supporting electrolyte
mixture. Half-wave potentials were measured as the average of anodic
and cathodic peak potentials.
Synthesis of 6. To a 250 mL flask containing 1 (0.2 g, 0.5 mmol)
and 3 (0.1 g, 0.5 mmol) was added 60 mL of dry CH2Cl2, and the
mixture was allowed to stir for 10 min at room temperature under a N2
atm. Then TFA (0.01 mL, 0.1 mmol) was added, and the mixture
allowed to stir for 45 min. After removal of the solvent, the crude
product was purified by silica gel column chromatography, 100−200
mesh. The first moving fraction eluted with EtOAc/petroleum ether
(3:97) was identified as yellow solid 6 in 28% yield. Spectral data for 6:
mp >250 °C; 1H NMR (300 MHz, CDCl3, 298 K, TMS) δ 8.21 (brs,
2H; NH), 6.78 (s, 2H; thienyl-β-CH), 5.98−5.96 (m, 2H; pyrrolic-β-
CH), 5.87−5.85 (m, 2H; pyrrolic-β-CH), 4.19−3.97 (m, 6H;
ferrocenyl CH), 3.35 (s, 2H; ferrocenyl CH), 1.73 (s, 12H; CH3),
1.62 (s, 6H; CH3), 1.26 (s, 6H; CH3); FAB-MS (m/z) calcd for
C34H40FeN2S 564.22, obsd 564.87 (100%, M+). Anal. Calcd (%) for
C34H40FeN2S: C 72.33, H 7.14, N 4.96. Found: C 71.25, H 7.17, N
4.87.
Synthesis of 7. The above procedure was followed by using 4
(0.092 g, 0.5 mmol). The first fraction eluted with EtOAc/petroleum
ether (3:97) was identified as yellow solid 7 in 27% yield. Spectral data
for 7: mp >250 °C; 1H NMR (300 MHz, CDCl3, 298 K, TMS) δ 8.36
(brs, 2H; NH), 6.05 (s, 2H; furanyl-β-CH), 5.96−5.95 (d, J = 2.7 Hz,
4H; pyrrolic-β-CH), 4.02−3.82 (m, 8H; ferrocenyl CH), 2.15 (s, 6H;
CH3), 1.65 (s, 18H; CH3); FAB-MS (m/z) calcd for C34H40FeN2O
548.25, obsd 548.60 (100%, M+). Anal. Calcd (%) for C34H40FeN2O:
C 74.45, H 7.35, N 5.11. Found: C 74.67, H 7.29, N 5.17.
Synthesis of 8. To a 250 mL flask containing 2 (0.2 g, 0.3 mmol)
and p-tolualdehyde (0.036 mL, 0.3 mmol) was added 100 mL of dry
CH2Cl2 under inert conditions, and the mixture was allowed to stir for
10 min at room temperature. TFA (0.0007 mL, 0.01 mmol) was added
to the above reaction mixture, and the solution allowed to stir for 2 h.
To the reaction mixture, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
Figure 4. Single-crystal X-ray structure of 11. (a) Top view, (b) side
view, (c) two-dimensional array. meso-Phenyl groups and the groups
that are not involved in the intermolecular hydrogen-bonding
interactions are omitted for clarity.
distances and angles are 2.56 Å, 161° and 2.79 Å, 124°,
respectively.
As observed in the case of 11, 9 also forms three self-
assembled dimers through intermolecular hydrogen-bonding
interaction, namely, (a) between the meso-p-cyano benzene
units; (b) one of the phenyl C−H units from the meso sp3
carbon with the meso-p-cyano benzene π-cloud; and (c) the
ferrocenyl C−H with one of the meso-phenyl unit's π-cloud.
The distances and angles are (a) C38−H38···N3: 2.56 Å, 148°;
(b) C50−H50···phenyl (π): 2.61 Å, 161°; and (c) C9−
H9···phenyl (π): 2.62 Å, 142°, where the self-assembled dimers
interact with each other to form a one-dimensional array (see
the Supporting Information). Further, combining such dimers
and the one-dimensional array, 9 generates a two-dimensional
supramolecular assembly in the solid state, which is shown in
Figure 5h. On the other hand, in 10, the β-CH protons of the
pyrrolic units (C14−H14 and C18−H18) that are present in
the dipyrrin moiety interact with one of the meso-phenyl unit's
π-cloud through intermolecular hydrogen-bonding interactions
to form the one-dimensional array (Figure 5i). The distances
and angles are 2.85 Å, 152° and 2.48 Å, 149°, respectively.
CONCLUSION
■
In summary, the synthetic protocol developed for ansa-
ferrocene-incorporated normal calixphyrins and core-modified
calixpyrroles and calixphyrins is straightforward due to the
absence of side products and easier purification. To the best of
our knowledge, this is the first report on ansa-ferrocene-based
core-modified calixpyrrole systems. The present work demon-
strates the incorporation of both ferrocene and thiophene/
furan simultaneously in the main framework of calixpyrroles
and calixphyrins. UV−vis absorption studies show the bands
due to dipyrrin and tripyrrin moieties. The structures of these
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Figure 5. Single-crystal X-ray structures and analyses of 8−10. (a, b; c, d; and e, f) Top and side views of 8−10 with intramolecular hydrogen-
bonding interactions. (g, i) One-dimensional arrays of 8 and 10. (h) Two-dimensional array of 9. meso-Phenyl groups and the groups that are not
involved in the intermolecular hydrogen-bonding interactions are omitted for clarity.
(0.14 g, 0.6 mmol) was added, and the solution was opened to air and
stirred for a further 2 h. The solvent was removed using a rotary
evaporator. The crude product was purified by silica gel column
chromatography (100−200 mesh), and the red fraction eluted with
CH2Cl2/petroleum ether (15:85) was identified as 8 in 18.5% yield.
Spectral data for 8: mp >250 °C; 1H NMR (300 MHz, CDCl3, 298 K,
TMS) δ 16.26 (brs, 1H; NH), 7.61 (m, 2H; phenyl CH), 7.4−7.38
(m, 9H; phenyl CH), 7.17−7.14 (m, 8H; phenyl CH), 6.96−6.93 (m,
5H; phenyl CH), 6.62−6.61 (d, J = 3.92 Hz, 2H; pyrrolic-β-CH),
5.81−5.80 (d, J = 4 Hz, 2H; pyrrolic-β-CH), 4.59 (s, 2H; ferrocenyl
CH), 3.9 (s, 2H; ferrocenyl CH), 3.86 (s, 2H; ferrocenyl CH), 2.89 (s,
2H; ferrocenyl CH), 2.45 (s, 3H; CH3); UV/vis (CHCl3) λmax (ε)
468.5 nm (33 000 mol−1 dm3 cm−1); FAB-MS (m/z) calcd for
C52H40FeN2 748.25, obsd 748.22 (100%, M+). Anal. Calcd (%) for
C52H40FeN2: C 83.42, H 5.38, N 3.74. Found: C 83.31, H 5.30, N
3.69.
Synthesis of 9. The above procedure was followed using 4-
cyanobenzaldehyde (0.04 g, 0.3 mmol). The red fraction eluted with
CH2Cl2/petroleum ether (40:60) was identified as 9 in 17% yield.
Spectral data for 9: mp >250 °C; 1H NMR (300 MHz, CDCl3, 298 K,
TMS) δ 16.18 (brs, 1H; NH), 7.78 (s, 4H; phenyl CH), 7.38 (s, 10H;
phenyl CH), 7.17−7.15 (t, 6H; phenyl CH), 6.96−6.95 (m, 4H;
phenyl CH), 6.48−6.47 (d, J = 4.04 Hz, 2H; pyrrolic-β-CH), 5.87−
5.85 (d, J = 3.8 Hz, 2H; pyrrolic-β-CH), 4.57 (s, 2H; ferrocenyl CH),
3.97 (s, 2H; ferrocenyl CH), 3.86 (s, 2H; ferrocenyl CH), 2.93 (s, 2H;
ferrocenyl CH); UV/vis (CHCl3) λmax (ε) 467.4 nm (38 000
mol−1 dm3 cm−1); FAB-MS (m/z) calcd for C52H37FeN3 759.23,
obsd 758.80 (100%, M+). Anal. Calcd (%) for C52H37FeN3: C 82.21, H
4.91, N 5.53. Found: C 82.15, H 4.97, N 5.41.
Synthesis of 10. The above procedure was followed using 9-
anthraldehyde (0.6 g, 0.3 mmol). The red fraction eluted with
CH2Cl2/petroleum ether (20:80) was identified as 10 in 19% yield.
1
Spectral data for 10: mp >250 °C; H NMR (300 MHz, CDCl3, 298
K, TMS) δ 16.41 (brs, 1H; NH), 8.55 (s, 1H; phenyl H), 8.17−8.05
(m, 4H; phenyl H), 7.48−7.39 (m, 14H; phenyl H), 7.14−7.12 (m,
6H; phenyl H), 6.96−6.93 (m, 4H; phenyl H), 5.98−5.97 (d, J = 4 Hz,
2H; pyrrolic-β-CH), 5.69−5.67 (d, J = 4 Hz, 2H; pyrrolic-β-CH), 4.76
(s, 2H; ferrocenyl CH), 4.01 (s, 2H; ferrocenyl CH), 3.90 (s, 2H;
ferrocenyl CH), 3.02 (s, 2H; ferrocenyl CH); UV/vis (CHCl3) λmax
(ε) 474.5 (190 000), 386 (94 000), 366.5 (95 700), 348.5 (71 000),
332 nm (49 700 mol−1 dm3 cm−1); FAB-MS (m/z) calcd for
C59H42FeN2 834.23, obsd 834.08 (100%, M+). Anal. Calcd (%) for
C59H42FeN2: C 84.88, H 5.07, N 3.36. Found: C 84.75, H 5.13, N
3.27.
Synthesis of 11. To a 250 mL flask containing 2 (0.2 g, 0.3 mmol)
and 5 (0.091 g, 0.3 mmol) was added 120 mL of dry CH2Cl2, and the
mixture was allowed to stir for 10 min at room temperature under N2
atm. Then TFA (0.005 mL, 0.06 mmol) was added, and the solution
allowed to stir for a further 2 h. To the reaction mixture was added 2,3-
dichloro-5,6-dicyano-1,4-benzoquinone (0.136 g, 0.6 mmol), and the
solution was opened to the air and stirred for a further 2 h. After
removal of the solvent, the crude product was purified by silica gel
column chromatography (100−200 mesh). The first fraction eluted
with CH2Cl2/petroleum ether (50:50) was identified as red solid 11 in
1
4% yield. Spectral data for 11: mp >250 °C; H NMR (500 MHz,
CDCl3, 298 K, TMS) δ 7.37 (m, 10H; phenyl CH), 7.26−7.22 (m,
10H; phenyl CH), 7.06−7.05 (m, 6H; phenyl CH), 6.84−6.83 (m,
4H; phenyl CH), 6.78−6.77 (d, J = 4.5 Hz, 2H; pyrrolic-β-CH), 6.74
(s, 2H; thienyl-β-CH), 6.64−6.63 (d, J = 4.5 Hz, 2H; pyrrolic-β-CH),
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5.86 (s, 2H; ferrocenyl CH), 4.14 (s, 2H; ferrocenyl CH), 3.66−3.65
(d, J = 1 Hz, 2H; ferrocenyl CH), 3.01 (s, 2H; ferrocenyl CH); UV/vis
(CHCl3) λmax (ε) 494.8 (38 000), 520 nm (41 000 mol−1dm3cm−1);
FAB-MS (m/z) calcd for C62H46FeN2S 904.26, obsd 904.68 (100%,
M+). Anal. Calcd (%) for C62H46FeN2S: C 82.11, H 5.11, N 3.09.
Found: C 82.01, H 5.09, N 3.04.
D. J. Angew. Chem., Int. Ed. 2000, 39, 1496−1498. (d) Turner, B.;
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J. Chem.Eur. J. 2002, 8, 3148−3156. (h) Cafeo, G.; Gargiulli, C.;
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X-ray Crystallography. The single-crystal X-ray diffraction data of
8−11 were collected on a Bruker SMART Apex diffractometer
equipped with a CCD area detector at 100(2) K, whereas those of 6
were collected on a Bruker AXS Kappa Apex 2 CCD diffractometer at
293(2) K. The data were refined by full-matrix least-squares
procedures with anisotropic thermal parameters for the non-hydrogen
atoms. The hydrogen atoms were calculated in ideal positions.
Structures were solved by using the Crystal Structure crystallographic
software package33 and SIR9734 and refined by full-matrix least-squares
on F2 with anisotropic displacement parameters for the non-hydrogen
atoms using SHELXL-97.35 Good-quality single crystals were grown
by slow evaporation of n-heptane into CHCl3 solutions of 6 and 8−11.
CCDC-816067 for 6, -816068 for 8, -816065 for 9, -816064 for 10,
and -816066 for 11 contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from the
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
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ASSOCIATED CONTENT
* Supporting Information
■
S
This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: srini@niser.ac.in. Fax: (+91)674-2302436.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
A.S. thanks the Directors of NIIST-CSIR and NISER for
financial support. S.R.K. thanks UGC for the fellowship. We
thank Dr. Babu Varghese, SAIF, IIT-Chennai, for solving the
crystal structure of 6. We greatly acknowledge Mrs. Viji and Mr.
Adarsh, NIIST-CSIR, for recording the FAB-MS and NMR
spectra.
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