Functional hybrid materials based on layered simple hydroxide hosts and dicarboxylate schiff base metal complex guests

Article abstract of DOI:10.1002/ejic.201200695

The insertion of carboxysalen-type complexes into magnetic layered transition-metal simple hydroxides has provided new hybrid compounds. Three kinds of carboxysalen ligands have been used: an ethylenediamine bridge (SED-H₂), a chiral cyclohexan

Full text of DOI:10.1002/ejic.201200695

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DOI: 10.1002/ejic.201200695
Functional Hybrid Materials Based on Layered Simple Hydroxide Hosts and
Dicarboxylate Schiff Base Metal Complex Guests
Séraphin Eyele-Mezui,[a] Emilie Delahaye,[a][‡] Guillaume Rogez,*[a] and Pierre Rabu*[a]
Keywords: Hybrid materials / Layered compounds / Schiff bases / Magnetic properties / Hydroxides
The insertion of carboxysalen-type complexes into magnetic
layered transition-metal simple hydroxides has provided new
hybrid compounds. Three kinds of carboxysalen ligands
have been used: an ethylenediamine bridge (SED-H2), a chi-
ral cyclohexanediamine bridge [(S,S)-SCD-H2 and (R,R)-
SCD-H2], and an aromatic o-phenylenediamine bridge (SBD-
logues to be overcome, namely hydrolysis and decomplex-
ation during the insertion reaction. Hence, in this work it was
possible to insert a wide variety of complexes into layered
simple hydroxides, including MIII complexes, for the first
time. The insertion of chiral carboxysalen complexes led to
the formation of chiral magnets in which chirality transfer to
H2). The ccorresponding CuII, NiII, CoII, ZnII, MnIII, and AlIII the inorganic layers was evidenced and seems to be favored
complexes were synthesized and inserted into layered cobalt
and copper hydroxides. The structural and spectroscopic in-
vestigations confirmed the successful insertion-grafting of
the complexes leading to new layered hybrid materials in
which the inserted complexes act as pillars between the inor-
ganic layers. The use of carboxylate anchoring functions en-
abled some of the difficulties encountered during the pre-
by the carboxylate anchoring groups. Finally, magnetic char-
acterization showed that the copper hydroxide hybrids ex-
hibit overall antiferrimagnetic behavior, whereas the cobalt
hydroxide hybrids present ferromagnetic ordering, with or-
dering temperatures ranging from 6.5 to 12.8 K. In this case
the nature of the cation inserted between the layers in-
fluences the magnetic behavior of the hybrid, contrary to
viously reported insertion of sulfonatosalen complex ana- what was observed in the case of the sulfonate analogues.
such as magneto-optical, photomagnetic, or magnetic and
supraconductive. Chemistry plays a major role in improving
Introduction
Nowadays, the controlled synthesis of hybrid materials is
of particular interest for the design of new materials with
specific chemical, physical, or biological properties.[1–13] For
example, the insertion of organic or organometallic species
into layered inorganic compounds can lead to original
nanosized organic/inorganic, inorganic/inorganic, or bio/
inorganic functional heterostructures.[14–30] Through the
multiscale organization of their components and because of
synergistic effects, such materials can acquire new proper-
ties not found elsewhere and become “multi-materials”, that
is, unique materials that simultaneously meet several
requirements. Layered systems, in which the properties of
each sub-network and their synergy can be tuned by the
topology and chemical bonding between constituents, have
been found to exhibit striking combinations of properties,
the interactions between organic and inorganic networks,
and it is essential to identify and control the structural
features and physical mechanisms influencing the properties
of these new hierarchically organized nanostructures.[13]
In recent work devoted to the methodical investigation
of hybrid organic/inorganic magnetic compounds and their
functionalization,[19] the special case of the insertion by
anion exchange of Schiff base disulfonates [M{salen-
(SO3)2}]2– and [M{(R,R)- or (S,S)-Cysalen(SO3)2}]2– (M =
Cu2+, Ni2+, Co2+, and Zn2+) into copper(II) and cobalt(II)
hydroxides, [Cu2(OH)3(DS)] and [Co2(OH)3(DS0)] (DS– =
–
dodecyl sulfate and DS0 = dodecyl sulfonate), was re-
ported.[31,32]
The structures of these compounds were established by
the combined use of X-ray powder diffraction (XRPD), ele-
mental analysis, FTIR and UV/Vis spectroscopy, and X-ray
photoelectron spectroscopy (XPS). Treatment of the start-
ing hydroxides with a solution of the nickel Schiff bases
[Ni{salen(SO3)2}]2– and [Ni{(R,R)- or (S,S)-Cysalen-
(SO3)2}]2– led to the substitution of the alkyl anions by the
nickel complexes retaining the structures of the parent
hydroxide layers.[31] We showed that the chirality of the Ni–
Cysalendisulfonates could be transferred to the whole hy-
brid structure to obtain a chiral magnet by design. This
approach is very promising for the construction of new
[a] IPCMS, UMR CNRS-UdS 7504,
23 rue du Loess, B. P. 43, 67034 Strasbourg Cedex 2, France
Fax: +33-3-88107247
E-mail: rogez@ipcms.u-strasbg.fr
rabu@ipcms.u-strasbg.fr
Homepage: http://www-ipcms.u-strasbg.fr/spip.php?article422
[‡] Current address: Institut de Chimie Moléculaire et des
Matériaux
d’Orsay, CNRS, Université Paris Sud 11,
91405 Orsay, France
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201200695.
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multifunctional layered compounds. The Schiff base metal plexed by Cu2+, Ni2+, Co2+, Zn2+, Mn3+, and Al3+, and
complexes are particularly appealing to this end, because then to discuss their properties and finally make a compari-
such complexes can be used in electroluminescent de- son with the disulfonate analogues. The influence of the an-
vices,[33–35] nonlinear optics,[36–40] electrochemical sen- choring moieties, sulfonate or carboxylate, on the stabilities
sors,[41,42] enantiocatalysis,[43,44] or as heterogeneous cata- of the complexes during the functionalization process and
lysts immobilized on polymers,[45] porous matrices,[46] or on the magnetic properties is emphasized. In this respect,
layered double hydroxides (LDHs).[47] In fact, we started to the results presented herein may be of broader significance,
generalize this approach by using salen- and Cysalensulfon- leading to a better interpretation of the properties of or-
ates of other metals.[32] However, the exchange reactions ganic/inorganic functional materials derived from transi-
were not as straightforward as for the nickel complexes. We tion-metal-based matrices incorporating functional molecu-
succeeded in inserting and grafting some Cu2+, Ni2+, Co2+
,
lar hosts.
and Zn2+ disulfonate complexes but, in some cases, cation
exchange took place. Partial decomplexation was observed
with exchange between the cations released by the com-
plexes and the cations of the hydroxide layers. In the copper
hydroxide analogues, such additional cation exchange led
to the transformation of the single octahedral CuII layers
into heterometallic triple-decker layers in the final products,
as depicted in Scheme 1.
Results and Discussion
Synthesis of the Schiff Base Complexes
We synthesized a series of salen-type Schiff base dicarb-
oxylate complexes in which the transition-metal ions lie in
the ONNO planar coordination site (Figure 1). The carb-
oxylate moieties are borne by the aromatic rings. The di-
amino bridges are simple ethylenediamine, chiral cyclohex-
anediamine, or the conjugated phenylenediamine.
The Schiff base ligands were synthesized by using modi-
fied literature procedures (see the Exp. Sect.)[48–54] by the
condensation of 2 equiv. of 3-formyl-4-hydroxybenzoic acid
(FBA-H)[48] with 1 equiv. of the corresponding diamine
(1,2-diaminoethane, 1,2-diaminobenzene, or chiral 1,2-di-
aminocyclohexane[52–54]).
The SED-H2 Schiff base ligand is only partially soluble
in polar solvents such as DMSO or DMF and insoluble in
alcohols and water. The dissolution of SED-H2 in an alk-
aline aqueous solution followed by complexation did not
give satisfactory results, except in the case of the complex-
Scheme 1. Insertion-grafting of disulfonatosalen-type complexes
into copper- and cobalt-layered hydroxides leads to drastic modifi-
cation of the structures and compositions of the inorganic layers.
This phenomenon has been ascribed to the destabiliza- ation of NiII. In the other cases we observed the formation
tion of the metal Schiff bases due to the presence of the of hydroxides or oxides, and/or the hydrolysis of the ligand.
sulfonate groups combined with the effect of the slightly Therefore, for the complexation of the CuII, CoII, and ZnII
alkaline character of the aqueous reaction medium.
metal ions, the ligand was partially solubilized in DMF[50]
Following these reports, this paper is intended first to before the addition of the corresponding metal acetate salt.
outline the synthesis and structures of two homologous The desired complexes were collected after precipitation
series of copper and cobalt hydroxides functionalized with with methanol. The FeIII complex was synthesized by an-
transition-metal salen- and Cysalendicarboxylates, com- other procedure,[55] namely by heating a suspension of
Figure 1. The salen-type Schiff bases used in this study (the nomenclature chosen indicates the protonation state of the carboxylate in
the as-synthesized ligands).
2
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Functional Hybrid Materials
SED-H2 in dry ethanol at reflux with 2 equiv. of triethyl- to lamellar compounds for which the elemental analysis
amine and adding anhydrous FeCl3 dissolved in dry eth- showed a clear excess of Fe. Mössbauer spectroscopy did
anol. Finally, the MnIII complex, SED-H2–MnCl was syn- not allow determination of the precise structures of the
thesized by heating SED-H2 and Mn(OAc)2·4H2O in meth- compounds, which are still under investigation.
anol at reflux with an excess of LiCl. MnII was oxidized to
MnIII in air, characterized by a change in color from yellow-
green to brown.
The potassium salt of the as-synthesized chiral ligand,
Structures of the Hybrid Compounds
SCD-K2, is soluble in both water and methanol. Therefore,
its complexation was easily performed by the addition of
an aqueous solution of the metal acetate salt (Co and Mn)
to a methanol solution of the ligand. The MnIII compound
was obtained upon oxidation in air in the presence of an
excess of LiCl.
All the compounds were characterized by ancillary tech-
niques, powder X-ray diffraction, elemental analysis, TGA/
TDA, FTIR, and UV spectroscopy.
The powder X-ray diffraction patterns of the starting
compounds and of the hybrid derivatives are shown in Fig-
ures 2 and 3 for the cobalt and copper hydroxide deriva-
tives, respectively.
SBD-H2 was complexed to CoII in DMF and to MnIII
in methanol (with an excess of LiCl). The AlIII complex,
SBD-H2–AlCl, was synthesized in ethanol under argon by
the reaction of SBD-H2 with Al(Et)2Cl.
Synthesis of the Hybrid Compounds
All the compounds were obtained by anion-exchange re-
actions starting from the cobalt or copper transition-metal
layered simple hydroxides prefunctionalized with dodecyl
–
sulfonate (DS0 ) or dodecyl sulfate (DS–), respectively (see
the Exp. Sect.). The formation of the intermediates
[Co2(OH)3(DS0)] and [Cu2(OH)3(DS)] led to an increase in
the interlamellar spacing (from 12.7 and 9.4 Å for
[Co2(OH)3(OAc)]·H2O and [Cu2(OH)3(OAc)]·H2O, respec-
tively, to 25.1 and 26.7 Å for [Co2(OH)3(DS0)] and
[Cu2(OH)3(DS)], respectively). This increase allows for
easier insertion-grafting of large molecules.[56] In addition,
the grafting of long alkyl chains within the interlamellar
space creates a local hydrophobic environment, which limits
the hydrolysis of the complexes being inserted.[31,32] The fi-
nal exchange reaction of the alkyl chains by the salencarb-
oxylate complexes took place in 1:1 water/ethanol, which
favored the solvation of the dodecyl sulfonate or dodecyl
sulfate when removed from the interlamellar space. Finally,
the temperature of the reaction was also an important pa-
rameter. All the reactions took place at reflux (around
80 °C). This temperature guaranteed the stability of the
Schiff base complexes during the anion-exchange reactions
and at the same time favored an efficient substitution rate
with complete removal of the dodecyl sulfonate or dodecyl
sulfate anions from the interlamellar space of the parent
hydroxides. In the case of the functionalization of copper
hydroxide, it was possible to proceed at a lower temperature
(60 °C), but in this case the reactions took much longer
(typically 24 h), and the crystallinity of the hybrids was not
as good.
Figure 2. Powder XRD patterns of the hybrid compounds based
on cobalt hydroxide (Cu-Kα1 = 1.540598 Å).
Most of the reactions were successful, yet all attempts to
insert/graft the SED-H2–Zn complex into cobalt hydroxide
led to mixtures of nonlamellar compounds. The insertion
of the SBD–AlCl complex into copper hydroxide led to the
In the low 2θ range (2θ Ͻ 35°), the diffraction patterns
formation of [Cu2(OH)3Cl]. The insertion of the SED-H2– of all the compounds show intense 00l diffraction lines up
FeCl complex into both cobalt and copper hydroxides led to at least the third harmonic, which evidences their lam-
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and 60° (Cu-Kα1 = 1.540598 Å), which suggests a similar
in-plane structure and a similar turbostratic disorder for all
the compounds. As shown previously for alkyl carboxylate
and alkyl sulfate derivatives,[57,58] the structure of the inor-
ganic layer in cobalt hydroxide systems can be described as
a triple-deck sheet deriving from the structure of the analo-
gous [Zn5(OH)8(NO3)2]·2H2O.[59,60] It is formed of a mono-
layer of octahedral CoII hydroxide (Brucite-type structure)
with metal vacancies counter-balanced by the occurrence
of tetrahedral CoII sites on both sides of the octahedral
monolayer.
Considering the thickness of the inorganic layer
(7.3 Å[58]), the basal spacing of the functionalized cobalt
hydroxide hybrids accounts well for the perpendicular inser-
tion into the inorganic layers of the salen-type complexes,
the size of which may be estimated to be about 15 Å from
published structures.[50]
For the copper compounds, as shown for the hybrid alkyl
carboxylate, alkyl sulfate, or alkyl sulfonate layered copper
hydroxides,[57,61–67] the structures of the inorganic layers
consist of a quasi-planar triangular array of octahedral
copper(II) ions.[68,69]
The basal spacings of the Cu–SED–M compounds (M =
Cu, Ni, Co, “MnCl”) are in good agreement with the sizes
of the SED-H2–M complexes and the thicknesses of the
inorganic layers (about 2.5 Å[68]). The noticeable exception
in this series concerns the case of the insertion of the SED-
H2–Zn complex, which leads to a lamellar material with a
much larger basal spacing (22.6 Å). Moreover, the XRD
pattern of this compound exhibits features at around 33
and 60°, similar to those observed in the cobalt hydroxide
derivatives and considered as typical of the formation of a
triple inorganic layer. The elemental analysis also shows a
net excess of Zn with respect to what is expected for a sim-
ple insertion-grafting of SED-H2–Zn. One hypothesis is
that this compound results from the partial decomplexation
of the SED-H2–Zn complex and the subsequent formation
of a heterometallic triple inorganic layer containing CuII in
an octahedral environment and ZnII in tetrahedral sites.
This phenomenon has already been described for the inser-
tion-grafting of the sulfonated analogue complex.[32]
The interlamellar distances observed after the insertion
of the other complexes, SCD-K2–M M and SBD-H2–M (M
= Co and “MnCl”), are also larger (by about 3 Å) than
expected for “simple” insertion-grafting of the complexes.
Yet, for these compounds, elemental analysis does not show
any excess of the metal cation from the starting complex,
and the XRD pattern does not show any peak correspond-
ing to the formation of a triple inorganic layer. Finally, we
noticed that thermal treatment of the compounds (heating
Figure 3. Powder XRD patterns of the hybrid compounds based
on copper hydroxide (Cu-Kα1 = 1.540598 Å).
ellar structure. The experimental basal distances are col- of the powder samples in an oven at 80 °C for 24 h) led to
lected in Table 1. All the compounds exhibit a marked shift the irreversible formation of dehydrated compounds with
of the 00l peak positions in comparison with the starting interlamellar distances of around 18.6 Å, in agreement with
materials.
what was obtained from the grafting of SED-H2–M M (M
The XRD patterns of all the cobalt derivatives, including = Co, Cu, Ni, “MnCl”; see the example of Cu-SCD–M
the starting compound [Co2(OH)3(DS)], exhibit similar fea- MnCl in Figure 3). Therefore, we propose that the as-syn-
tures in the region of the in-plane diffraction lines (high 2θ thesized copper hydroxide compounds are actually hydrated
angles) with characteristic asymmetrical peaks at 2θ = 33 compounds, with water in the interlamellar space and
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Functional Hybrid Materials
Table 1. Experimental basal spacing in the hybrid compounds.
Co hydroxide hybrid compound
d00l [Å]
Cu hydroxide hybrid compound
d00l [Å]
Co–SED–Cu
Co–SED–Ni
Co–SED–Co
Co–SED–Zn
22.4
22.3
22.3
Cu–SED–Cu
Cu–SED–Ni
Cu–SED–Co
Cu–SED–Zn
18.6
18.6
18.6
22.6
nonlamellar compound
Co–SED–MnCl
Co–SCD–Co
Co–SCD–MnCl
22.3
22.4
22.1
Cu–SED–MnCl
Cu–SCD–Co
Cu–SCD–MnCl
18.6
20.8
20.9/18.6 after thermal treatment
Co–SBD–Co
Co–SBD–MnCl
Co–SBD–AlCl
22.4
22.6
22.3
Cu–SBD–Co
Cu–SBD–MnCl
21.4
21.6
strongly involved in hydrogen bonding, which prevents the
connection of all of the carboxylate groups of the com-
plexes and increases the interlamellar spacing (Scheme 2).
Scheme 2. Evolution of the structures of the Cu–SCD–M and Cu–
SBD–M compounds and their influence on the basal spacing upon
dehydration.
Figure 4. FTIR spectra of the hybrid compound Co–SBD–Co, the
parent compounds SBD-H2 and SBD-H2–Co, and the cobalt hy-
droxy dodecyl sulfonate [Co2(OH)3(DS0)].
Yet it appears that in most cases this dehydration process
degrades the crystallinity of the materials. Therefore, in the
following we will focus on the hydrated samples, which were
found to remain stable (and hydrated) for several weeks.
Note that no 00l diffraction lines from the starting hy-
droxides [Co2(OH)3(DS0)] and [Cu2(OH)3(DS)] were evi-
denced, which indicates the completeness of the reactions.
This was further confirmed by FTIR spectroscopy (see be-
low) and elemental analysis (see the Exp. Sect.). The inser-
tion rates, determined from the elemental analyses, are in
the same range for all compounds, ranging from 0.2 to 0.35
inserted complexes per Co or Cu ion of the hydroxide host.
After the exchange reaction, the spectra of all the hybrids
indicate the almost complete disappearance of the very
strong CH and CH2 absorption bands at ν = 2925 and
˜
2854 cm–1 and the vanishing of the –SO3 or –SO4 bands at
ν = 1300–1000 cm–1 arising from the dodecyl sulfate or do-
˜
decyl sulfonate in the copper or cobalt hydroxide precur-
sors, respectively.[31,32,77] Concomitantly, characteristic
bands of the Schiff base complexes are observed, for which
the data are summarized in Table SI1 in the Supporting In-
formation.
A sharp and strong absorption band assigned to the im-
ine C=N group is observed at ν = 1616 cm–1 for the free
˜
ligands SBD-H2, SED-H2, and SCD-K2. A set of vibrations
assigned to aromatic C=C group is detected in the range ν
˜
= 1580–1430 cm–1.[76] The vibrations of the phenol groups
appear in the range 1120–1200 cm–1. The antisymmetrical
and symmetrical vibrations of the carboxyl functions are
FTIR Spectroscopy
The FTIR spectra of the Schiff base complex based hy- observed at νas = 1680–1700 cm–1 and ν = 1380–1401 cm–1
˜
˜
s
brids exhibit common features (see the Supporting Infor- for the SBD-H2 and SED-H2 derivatives. The difference be-
mation). Typical spectra of the hybrid compounds, the com- tween the two components Δν is 268–326 cm–1. In the carb-
˜
plex, and the hydroxide precursors are presented in Fig- oxylate salt SCD-K , ν shifts to 1627–1640 cm–1 due to
˜
2
as
ure 4. The complete list of absorption bands is given in coordination to potassium, and Δν = 233–264 cm–1. The
Table SI1 in the Supporting Information. Assignments were characteristic bands of the C=C and C–C bonds of the
made by comparison with the literature.[70–76]
phenyl, ethylene, benzene, or cyclohexanediamine groups
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are observed in the regions 1450–1580 and 1230–1330 cm–1. on the differential thermal and gravimetric analysis (DTA/
The energies of the vibrations are slightly higher for the TGA) of the cobalt hydroxide based systems. The copper
SBD and SCD than for the SED compounds. The absorp- hydroxide analogues exhibit a similar behavior. The thermal
tions at 1122–1136 and 1180–1197 cm–1 have been assigned decomposition of Co–SED–MnCl, Co–SCD–MnCl, and
to C–O. All compounds, including the starting ligands and Co–SBD–MnCl is presented in Figures SI4 and SI5 in the
their complexes, exhibit strong and very broad IR absorp- Supporting Information as examples. The results indicate
tion bands in the regions 3450–3000 cm–1 [ν(OH)] and that the decomposition occurs in two stages.
1030–1089 cm–1 [δ(OH)], which have been ascribed to the
The first weight loss is observed between ambient tem-
significant presence of lattice water and hydrogen bonds. perature and 160 °C. This first decrease of 11–15% corre-
After complexation with transition-metal ions, additional sponds to the loss of water molecules, in agreement with
bands, slight shifts, or variation of intensities were ob- the chemical formulae of the compounds. This step is ex-
served. However, no systematic variation can be identified tended to temperatures much higher than 100 °C, which in-
in these sets of superimposed absorption signals. M–N and dicates that some of the water molecules interact strongly
M–O bands are observed at high energy in the region 420– with the inorganic layers. The latter can be involved in a
665 cm–1.
hydrogen-bonding network. This is markedly true in the
After grafting the salens onto the hydroxide layers, one cases of Co–SCD–M and Cu–SCD–M, for which the re-
notices the systematic shift of the antisymmetrical vibration lease of water is observed up to 160 °C.
of the carboxylate functions [νas(COO)] to higher energy
The second step is observed between 150 and 300 °C
leading to Δν values similar to those observed for the potas- with a weight loss of 38–40%. This loss has been assigned
˜
sium salts. This observation is consistent with a unidentate to the degradation of the inserted metal complexes and in-
coordination of the carboxylate moieties to the metal ions organic layers in an exothermal process, as shown in the
in the hydroxide layers with possible hydrogen bonding to TDA plots.
pendant hydroxy groups.[78,79] Moreover, the typical very
At 900 °C, the final product is a black powder consisting
strong signals of the C–H vibrations (ν = 2925 and of a mixture of Co3O4 or CuO with MnO2, or other mixed
˜
2854 cm–1) and those stemming from the dodecyl sulfates spinel oxides Co3–xMxO4 (M = Cu, Mn, Ni, Fe, Zn).
or dodecyl sulfonates in the copper or cobalt hydroxide pre-
As emphasized before, specific thermal variation of the
cursors (ν = 1300–1000 cm–1) systematically vanish in the interlayer distances was observed for the Cu–SCD–M and
˜
hybrid compounds. Concomitantly, characteristic bands of Cu–SBD–M compounds. The TGA/DTA curves of Cu–
the Schiff base complexes are observed, which are summa- (S,S)-SCD–Co are shown as examples in Figure SI6 in the
rized in Table SI1 in the Supporting Information. These fea- Supporting Information. One notices a weight loss due to
tures support the complete anion exchange of the alkyl the release of water molecules up to 160 °C, which indicates
anions by the Schiff base complexes.
a strong interaction with the inorganic layers. The evolution
of the XRD patterns after “annealing” at 80 °C for 24 h
indicates that these water molecules can be released by long
thermal treatment at a lower temperature.
Scanning Electron Microscopy
The hybrid compounds were obtained as thin platelet-
shaped microcrystals, in agreement with the lamellar char-
acter of their structures. The morphologies and sizes of the
microcrystals are very similar to those of the starting mate-
rials, in agreement with the powder X-ray diffraction pat-
terns (Figure 5). Furthermore, the composition analysis by
EDX (cartography of a 104 μm2 area along with several
1 μm2 spot analyses) underlines the homogeneity of the dif-
ferent compounds.
UV/Vis Spectroscopy
The electronic transitions of the salen ligands, their com-
plexes, and the layered hybrids were identified by UV/Vis
spectroscopy. We present in Figures 6, 7, and 8 the spectra
recorded for copper and cobalt hydroxides functionalized
with some of the complexes. For a given ligand, other metal
complexes exhibit similar features.
In the UV region, the intense absorptions of the Schiff
base molecules can be attributed to π–π* transitions corre-
sponding to the conjugation of imine with the aromatic
rings and to the aromatic rings themselves superimposed
upon the n–π* transition of the azomethine.[80] In the case
of SBD-H2, these bands are broadened and shifted towards
smaller energies compared with SED-H2 and SCD-K2 due
to the additional conjugation induced by the aromatic
bridge.
Figure 5. SEM image of Co–(R,R)-SCD–Co (left) and Cu–(S,S)-
SCD–Co (right).
The corresponding complexes exhibit d–d transitions in
the visible region. For instance, SED-H2–Ni exhibits a tran-
Thermal Analysis
The thermal stabilities of all the hybrid compounds were sition at λ = 550 nm assigned to the d–d transition of NiII
investigated in air up to 900 °C. We essentially focus here ions (dxyǞdx2–y2, that is, 1A1Ǟ1B1 in C2v symmetry).[81] For
6
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Functional Hybrid Materials
Figure 6. Solid-state UV/Vis absorption spectra of SED-H2 (full
line), SED-H2–Ni (dashed line), Co-SED–Ni (spaced dotted line),
and Cu–SED–Ni (closely dotted line).
Figure 8. Solid-state UV/Vis absorption spectra of SBD-H2 (full
line), SBD-H2–AlCl (dashed line), Co–SBD–AlCl (spaced dotted
line), and Cu–SCD–AlCl (closely dotted line).
other two, at around 640 and 1550 nm, can be attributed to
d7 CoII ions in tetrahedral sites [4A2(F)Ǟ4T1(P) and
4A2(F)Ǟ4T1(F) transitions, respectively].[82] These features
are in accordance with the proposed structures and with
the magnetic behavior (see below).[59,83] The d–d transition
of the NiII ion appears as a shoulder at 520 nm. In the case
of the insertion of Mn or Co complexes, absorption due to
the cobalt ions of the inorganic layers hides the d–d transi-
tions of the metals of the inserted complexes.
In the copper hydroxide series, the broad absorption
band centered at λ ≈ 560 nm, typical of the CuII ion in the
octahedral geometry (2EgǞ2T2g), also masks the transitions
of the metals of the inserted complexes.
Optical Circular Dichroism
The two SCD-based series [(R,R) and (S,S)] give iden-
tical UV spectra. The optical circular dichroism (OCD)
spectra of the hybrid compounds show that the insertion of
a chiral complex leads to chiral hybrid compounds (Fig-
ure 9). The chirality is evidenced by the symmetry of the
Figure 7. Solid-state UV/Vis absorption spectra of SCD-K2 (full
line), SCD-K2–MnCl (dashed line), Co–SCD–MnCl (spaced dot-
ted line), and Cu–SCD–MnCl (closely dotted line).
the cobalt and manganese complexes, large bands at around OCD spectra of Cu–(R,R)-SCD–MnCl and Cu–(S,S)-
600 nm appear and can be assigned to the d–d transition of SCD–MnCl [and of Co–(R,R)-SCD–MnCl and Co–(S,S)-
the complexed metal [4T1g(F)Ǟ4T1g(P) for the CoII com- SCD–MnCl]. Three regions can be distinguished in the
5
plexes, and EgǞ5T2g for the MnIII complexes].[80]
spectra. Below 300 nm, the dichroic signal of the hybrid
Finally, in the copper and cobalt hybrid hydroxides, the compounds is almost zero, whereas it is quite strong in the
electronic transitions of the complexes overlay the transi- complex alone (see Figure SI7 in the Supporting Infor-
tions arising from the inorganic structures. In the UV re- mation) because of the strong OǞM charge transfer (M =
gion, the charge transfer OǞM (M = Co or Cu) of the Co or Cu) of the inorganic layers in this region. The signals
inorganic layers is superimposed upon the ligand transi- between 300 and 500 nm correspond to the dichroic signals
tions. For the cobalt hybrids (particularly visible in the of the π–π*, n–π*, and d–π* transitions of the inserted com-
spectrum of Co–SED–Ni), four additional bands are ob- plex. In the third region, above 500 nm, the sign of the sig-
served in the Vis/NIR region. Two of the bands, at around nal depends on the hydroxide host (Co or Cu), whereas the
580 and 1200 nm, have been attributed to high-spin (HS) sign of the signal in the high-energy region remains the
d7 CoII ions in octahedral sites [4T1g(F)Ǟ4T1g(P) and same irrespective of the metal cation of the inorganic host.
4T1g(F)Ǟ4T2g(F) transitions, respectively], whereas the Moreover, the OCD spectra of the hybrids in this region
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exhibit signs and shapes different to those of the complexes increase in the magnetization was observed at low fields,
alone. Therefore, this low-energy signal cannot be assigned and the magnetization value at high field was almost satu-
5
only to the EgǞ5T2g transition of the MnIII complex, but rated, but low and far from the expected value for full align-
may result from a combination of signals arising from the ment of the moments borne by the copper ions and the
inserted complex and the d–d transitions of the cations inserted complexes. The low-temperature ac susceptibility
within the hydroxide layers. This combination was not ob- measurements showed only the basis of growing peaks in
served in the case of the insertion of chiral salensulfonate the χЈЈ (out-of-phase susceptibility) signals, which indicates
complexes.[31] Such an interaction suggests that the carb- that long-range order is not fully established at 1.8 K.
oxylate groups are more efficient than sulfonates for a real
chirality transfer from the salen to the inorganic layers.
All of the cobalt hydroxide based hybrid compounds ex-
hibit similar behavior. Selected characteristic data are col-
lected in Table 2. The Curie constants are in agreement with
the proposed formulae (see the Exp. Sect.), considering a
contribution of 2.2–2.8 emuKmol–1 for the CoII ions in
tetrahedral sites, 2.8–3.4 emuKmol–1 for the CoII ions in
octahedral sites,[84] and the usual values for the transition
metal of the complexes inserted in between the inorganic
layers.
Table 2. Magnetic characteristics of the cobalt hybrid compounds.
Compound
C
TN
[K]
μ0HC
[T]
M5T [μB]
[emuKmol–1]
Co2(OH)3DS0
Co–SED–Cu
Co–SED–Ni
Co–SED–Co
Co–SED–MnCl
Co–(R,R)-SCD–Co
Co–(R,R)-SCD–MnCl
Co–SBD–MnCl
Co–SBD–Co
5.04
5.23
4.99
5.69
8.14
5.70
6.12
8.55
7.06
5.56
6.7
12.8
10.4
7.5
6.8
7.2
6.5
9.6
6.8
6.8
0.14
0.30
0.25
0.09
0.08
0.09
0.07
0.07
0.07
0.06
2.08
2.24
2.10
2.98
3.87
3.30
3.26
3.60
3.79
3.47
Co–SBD–AlCl
As an example, we report in Figures 10, 11, and 12 the
results concerning Co–SED–Cu. As the temperature de-
creases from room temperature, the χT product slightly de-
creases to a minimum at around 90 K. This small decrease
is well understood on the basis of a single-ion spin–orbit
coupling effect and/or antiferromagnetic interactions be-
tween the CoII moments. Below this minimum, the χT prod-
Figure 9. Solid-state OCD spectra of Co–(R,R)-SCD–MnCl (full
line) and Co–(S,S)-SCD–MnCl (dashed line) (above) and Cu–
(R,R)-SCD–MnCl (full line) and Cu–(S,S)-SCD–MnCl (dashed
line) (below).
Magnetic Properties
All copper hydroxide based hybrid compounds except for
Cu–SED–Co and Cu–SBD–Co show an overall antiferro-
magnetic behavior without ordering down to 1.8 K irre-
spective of the nature of the complex inserted (see the Sup-
porting Information). For Cu–SED–Co and Cu–SBD–Co,
the χT versus T curves suggest a weak ferrimagnetic order-
ing at very low temperature (ferromagnetic or canted anti-
ferromagnetic). This behavior was confirmed by the magne-
Figure 10. χT vs. T curve for Co–SED–Cu (under 500 Oe applied
tization versus field measurements at 1.8 K. A rather sharp dc field).
8
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Functional Hybrid Materials
uct exhibits a steep increase to a maximum at 11.3 K there are indeed important differences in the ordering tem-
(71 emuKmol–1). This increase can be related to the occur- peratures for a given organic ligand when the inserted metal
rence of long-range ferromagnetic order (Figure 10).
ion is changed. This indicates that the inserted cations par-
ticipate, at least partly, in the establishment of the magnetic
ordering, which suggests the occurrence of a noticeable
magnetic exchange interaction between the inorganic layers
and the inserted complexes. Note that the analogue hybrids
involving disulfonate complexes showed almost no in-
fluence of the inserted cation on the magnetic ordering tem-
peratures.[31,32] Thus, it appears that carboxylate anchoring
functions are more efficient than sulfonate groups in pro-
moting magnetic interactions and hence in controlling the
magnetic behavior of the hybrid systems.
Conclusions
In our previous work on the functionalization of layered
single metal hydroxides (LSHs) with metal complexes we
were able to insert some salendisulfonate complexes. Ini-
tially, the sulfonate anchoring groups were chosen to facili-
tate the dissolution of the complexes in water. Yet our re-
sults highlighted some limitations. First, the disulfonate
Schiff base complexes were found to be sensitive to hydroly-
sis during the anion-exchange reactions carried out in aque-
ous media. To limit hydrolysis, we developed a new ap-
proach involving the pre-insertion of long alkyl chain sulf-
onates or sulfates. As a result, the interlamellar space was
greater and more hydrophobic. Secondly, concomitant cat-
ion exchange with the metal of the hydroxide layers was
observed in some cases, inducing a significant change in the
structure of the inorganic host. To overcome this, we de-
cided to functionalize the LSH with dicarboxylate com-
plexes, which were expected to be more stable. Moreover, it
was particularly interesting to investigate the influence of
the anchoring groups (carboxylates versus sulfonates) on
the properties of the hybrid systems.
Figure 11. ac susceptibility measurements for Co–SED–Cu
(0.35 mT, 100 Hz; open circles: in-phase susceptibility; open
squares: out-of-phase susceptibility).
In this work we synthesized numerous transition-metal
Schiff base dicarboxylate complexes, including complexes
of trivalent metals. These complexes were successfully in-
serted and grafted into copper and cobalt LSHs. No hydrol-
ysis occurred, and we observed no double exchange except
with the Cu–SED–Zn system. In fact, the zinc complex is
Figure 12. M vs. H curve for Co–SED–Cu at 1.8 K.
The ordering temperatures were determined by ac the more labile one. Hence, the carboxylate moieties really
susceptibility measurements (f = 100 Hz, μ0Hac = 0.35 mT, improve the robustness of the salen complexes in compari-
Figure 11). The maximum of the real part, χЈ, leads to a TN son with the sulfonates. Another difference of the sulfonate
value of 12.8 K for Co–SED–Cu.
analogues concerns the interaction of the complexes with
The ferromagnetic-type behavior is confirmed by the the inorganic host. We noticed that the magnetic ordering
magnetization versus field curve at low temperature (Fig- temperature of the cobalt hydroxide hybrids varies with the
ure 12), which shows the presence of a hysteresis loop with metal in the series of complexes studied in this work. This
a coercive field of 0.3 T at 1.8 K. The low value of the mo- was not the case for the sulfonate analogues, which indi-
ments at high field compared with that expected for a total cates a better coupling with the carboxylates than with the
alignment of the moments (4–6 μB for two CoII plus the sulfonates. The sulfonate group is usually known as a ligand
expected value for the inserted metal ion) confirms the ferri- that hampers efficient magnetic coupling.[85,86] This differ-
magnetic ordering.
ence is merely a result of the higher spin density along the
Despite the fact that there is no clear general tendency C–C bond of the carboxylates than along the C–S bond
in the evolution of the magnetic properties of the hybrids of the sulfonates within the anchoring moieties.[86–88] Thus,
depending on the inserted complex, it is worth noting that functionalization through carboxylate bridges is more ef-
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operating at 3 kV in the SEI mode. FTIR spectra were collected
with a Digilab FTS 3000 computer-driven instrument (0.1 mm
thick powder samples ca. 1% in KBr) in transmittance with a reso-
lution of 4 cm–1 [software: Digilab Merlin 3.4; laser He-Ne; detec-
tor MCT (Cryogenic Mercury CadmiumTellurid); source: standard
ceramic]. UV/Vis/NIR studies were performed with a Perkin–Elmer
Lambda 950 spectrometer (spectra recorded in reflection mode
using a 150 mm integrating sphere with a mean resolution of 2 nm
and a sampling rate of 300 nmmin–1). Optical circular dichroism
spectra were recorded as powders diluted in KBr pellets (ca. 1%
ficient for the tuning of the magnetic properties of these
layered hybrid systems, all the more so as we can vary the
metal ion in the salen complexes.
More generally, immobilization and grafting into the
layered hydroxides of such a variety of metal complexes
with different functionalities gives, in principle, many pos-
sibilities for adapting these hybrid materials to different ap-
plications. Some possibilities were investigated. Concerning
the transfer of chirality, the carboxylate group again seems
more efficient than the sulfonate. As a possible application, weight) with a Jasco 810 spectrometer. The data were corrected for
the background signal of a pellet of pure KBr of the same dimen-
sions. TGA/TDA experiments were performed by using a Texas
Instruments SDT Q600 instrument (heating rates of 5 °Cmin–1, air
stream, platinum crucible). Magnetic studies were performed with
a SQUID magnetometer (Quantum Design MPMS-XL) in the
temperature and field ranges of 2–300 K and Ϯ5 T, respectively; ac
susceptibility measurements were performed in a 0.35 mT alterna-
tive field (100 Hz). Magnetization measurements at different fields
at room temperature confirmed the absence of ferromagnetic impu-
rities.
we tested the enantiocatalytic activity of M–[(R,R)- or
(S,S)]-SCD–MnCl (M = Cu or Co) in the epoxidation of
styrene. The hybrid system was stable under the alkaline
and oxidative conditions of the reaction. Nevertheless, we
observed no significant activity, contrary to what was re-
ported by Bhattacharjee et al. for Zn-Al layered double hy-
droxide based systems.[20] This difference could arise from
the different specific area and accessibility of the salen com-
plex embedded within the hydroxide host. Recently, we have
shown in peptide inserted hydroxides that molecules in-
serted in LSH are accessible to small ions.[16] We envision
testing the chiral compounds of this study for catalytic ac-
tivity towards molecules in the gas phase.
We also investigated the optical properties of the hydrox-
ides encompassing Al3+ salen complexes, which have been
reported to show intense blue luminescence with adjustable
quantum yields.[48] In the hybrid structures, the lumines-
cence was apparently quenched as a result of absorption by
the inorganic layers. Such quenching was also observed in
LSHs containing oligothiophenedicarboxylates[89] whereas
photoluminescence was maintained in oligo(phenylene–
vinylene) (OPV) systems.[29] Our results indicate that the
emission wavelengths of the molecular dyes and their dis-
tance to the inorganic layers has to be adjusted in order
to obtain luminescent hybrids. This could be achieved by
appropriate modification of the complexes. For instance,
longer carboxylate anchoring arms can be grafted onto the
salen core. Several other applications can be explored for
these new hybrid multifunctional systems depending on the
metal ions involved in the complex. As a result of the cur-
rent improvements in the control of the anion-exchange re-
action we have shown that the insertion and grafting of
metal complexes into layered single metal hydroxides is a
tractable and appealing approach towards new functional
materials.
Synthesis of [Cu2(OH)3(C12H25SO4)]·0.5H2O and [Co2(OH)3-
(C12H25SO3)]: [Co2(OH)3(DS0)] and [Cu2(OH)3(DS)] were synthe-
sized according to protocols published in previous works.[58,63] All
experiments were conducted under argon, and the solvents were
degassed prior to use. The yields of the hybrid compounds were
around 50–70%.
Ligand Synthesis
3-Formyl-4-hydroxybenzoic Acid (FBA-H): 3-Formyl-4-hydroxy-
benzoic acid was synthesized according to a published pro-
cedure.[48] In
a
500 mL flask, p-hydroxybenzoic acid (15 g,
108 mmol) was added to trifluoroacetic acid (40 mL) to form a
suspension. solution of hexamethylenetetraamine (15.3 g,
A
109 mmol) in trifluoroacetic acid was added dropwise under Ar.
After heating at reflux under Ar for 2 h, the reaction mixture
turned a transparent yellow. After cooling to ambient temperature,
the solution was stirred with 4 m HCl (300 mL) for 3 h. The yellow-
ish solid was filtered, washed with water (10ϫ 100 mL), and dried
under vacuum. Yield: 40%. 1H NMR (300 MHz, [D6]DMSO): δ =
7.06 (d, J = 8.82 Hz, 1 H), 8.0 (dd, J1 = 2.43, J2 = 8.82 Hz, 1 H),
8.21 (d, J = 2.22 Hz, 1 H), 10.28 (s, 1 H) ppm. C8H6O4·0.2H2O
(169.73): calcd. C 56.75, H 3.76; found C 56.72, H 3.88.
Salendicarboxylic Acid (SED-H2): FBA-H (1.08 g, 6.5 mmol) was
dissolved in ethanol (30 mL), and a solution of ethylenediamine
(217 μL, 3.25 mmol) in ethanol (30 mL) was added dropwise. The
reaction led to a yellow-orange precipitate. The mixture was heated
at reflux for 1 h and then cooled to room temperature. SED-H2
was isolated by filtration, washed with ethanol, and dried under
1
vacuum. Yield: 50%. H NMR (300 MHz, [D6]DMSO): δ = 3.94
(s, 4 H), 6.83–6.87 (d, J = 8.82 Hz, 2 H), 7.82–7.86 (dd, J1 = 2.22,
J2 = 8.61 Hz, 2Hb), 8.03–8.05 (d, J = 2.01 Hz, 2 H), 8.71 (s, 2 H)
ppm. C18H16N2O6·0.8H2O (371.3): calcd. C 58.22, H 4.76, N 7.54;
found C 58.22, H 4.87, N 8.12.
Experimental Section
Methods: Elemental analyses for C, H, N, S, and metals were car-
ried out by the Service de Microanalyses of the University of Stras-
bourg and by the Service Central d’Analyse of the CNRS (USR-
59). The powder XRD patterns were collected with a Bruker D8
ADVANCE diffractometer (Cu-Kα1, λ = 1.540598 Å) equipped
with the energy discriminating detector SolX. 1H NMR spectra
were recorded with a Bruker AVANCE 300 (300 MHz) spectrome-
ter. The peaks of nondeuteriated solvents were used as internal
references. The SEM images were obtained with a JEOL 6700F
scanning electron microscope equipped with a field emission gun
Dipotassium (R,R)-Cysalendicarboxylate [(R,R)-SCD-K2]: Dipotas-
sium (R,R)-cyclohexanediamine monotartrate (2.64 g, 10 mmol)
was dissolved in water/MeOH (60 mL, 1:1, v/v) along with K2CO3
(2.76 g, 20 mmol). An ethanolic solution (60 mL) of FBA-H
(3.32 g, 20 mmol) was added dropwise leading to a precipitate. Af-
ter complete addition, the reaction mixture was heated at reflux for
1 h and filtered immediately. The filtrate was concentrated to yield
a solid, which was recrystallized from ethanol. Yield: 91%. [α]2D0
+150 degdmϪ1 cm3 gϪ1 (c = 0.001 molL–1, methanol). 1H NMR
=
10
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Functional Hybrid Materials
(300 MHz, [D6]DMSO): δ = 1.45–9 (m, 8 H), 3.49 (s, 2 H), 7.69–
was reduced to 1/2 by concentration under reduced pressure. The
7.74 (dd, J1 = 1.98, J2 = 8.37 Hz, 2 H), 7.79–7.8 (d, J = 1.77 Hz, complex was then precipitated with diethyl ether, filtered, washed
2 H), 8.48 (s, 2 H) ppm. C22H20K2N2O6·2.8H2O (535.72): calcd. C
49.32, H 4.76, N 5.23; found C 49.29, H 4.35, N 5.18.
with diethyl ether, and dried under vacuum. Yield: 84%.
C18H14ClFeN2O6·0.5H2O (454.48): calcd. C 47.57, H 3.33, N 6.16;
found C 47.55, H 4.16, N 6.83.
Dipotassium (S,S)-Cysalendicarboxylate [(S,S)-SCD-K2]: The same
procedure as above was used, starting from dipotassium (S,S)-
cyclohexanediamine monotartrate. [α]2D0 = –174 degdmϪ1 cm3 gϪ1 (c
= 0.001 molL–1, methanol).
Synthesis of Complexes with SCD-K2
The procedures were the same for both the (R,R) and (S,S) enantio-
mers.
Phenylenesalendicarboxylic Acid (SBD-H2): o-Phenylenediamine
(0.36 g, 3.3 mmol) was dissolved in methanol (30 mL). A meth-
anolic solution (40 mL) of FBA-H (1.1 g, 6.6 mmol) was added
leading to the formation of a precipitate. After stirring at ambient
temperature for 2 h, the volume of the mixture was reduced to 1/3
by concentration under reduced pressure. The solid was collected
by filtration, washed with ethanol and diethyl ether, and dried un-
der vacuum. Yield: 57%. 1H NMR (300 MHz, [D6]DMSO): δ =
7.01–7.05 (d, J = 8.82 Hz, 2 H), 7.41–7.45 (m, 2 H), 7.50–7.54 (m,
2 H), 7.93–7.97 (m, 2 H), 8.33–8.35 (m, 2 H), 9.06 (s, 2 H) ppm.
C22H16N2O6·0.8H2O (418.98): calcd. C 63.06, H 4.76, N 6.68;
found C 62.99, H 4.42, N 7.34.
SCD-K2–MnCl: Mn(OAc)2·4H2O (0.77 g, 3.12 mmol) dissolved in
water (20 mL) was added rapidly drop-by-drop to a freshly pre-
pared solution of SCD-K2 (1.67 g, 3.12 mmol) in methanol
(20 mL). A greenish precipitate formed immediately. Then a satu-
rated aqueous solution of LiCl (3 mL) was added. The mixture was
then stirred at room temperature for 2 h, then left to stand for 2 h.
The solid was filtered, washed with water and ethanol, and dried
under vacuum. Yield: 41%. C22H18N2O6MnCl·8H2O (636.6):
calcd. C 41.63, H 5.69, N: 4.62; found C 41.51, H 5.38, N 4.36.
SCD-K2–Co: Co(OAc)2·4H2O (0.26 g, 1.03 mmol) dissolved in
water (20 mL) was added rapidly drop-by-drop to a methanolic
solution (40 mL) of SCD-K2 (0.55 g, 1.03 mmol). A brown precipi-
tate formed immediately, and the mixture was stirred at room tem-
perature for 2 h. The solid was filtered, washed with methanol, and
dried under vacuum. Yield: 90%. C22H18CoN2O6·6.4H2O (579.87):
calcd. C 45.56, H 5.34, N 4.36; found C 45.63, H 5.16, N 4.88.
Synthesis of Complexes with SED-H2
SED-H2–Co: SED-H2 (0.17 g, 0.46 mmol) was partially dissolved
in DMF (40 mL) under argon. Then a solution of Co(OAc)2·4H2O
(84 mg, 0.42 mmol) in DMF (40 mL) was added dropwise under
argon. The solution turned a clear blue. A brown solid precipitated
upon addition of methanol (100 mL), which was collected by fil-
tration, washed with methanol, and dried under vacuum. Yield:
65%. C18H14N2O6Co·2.7DMF (610.35): calcd. C 51.36, H 5.43, N
10.78; found C 51.19, H 5.27, N 10.72.
Synthesis of Complexes with SBD-H2
SBD-H2–MnCl: Mn(OAc)2·4H2O (0.44 g, 1.80 mmol) dissolved in
water (10 mL) was added dropwise to a methanolic suspension
(20 mL) of SBD-H2 (0.75 g, 1.80 mmol) with a few drops of NaOH.
Then a saturated aqueous solution of LiCl (3 mL) was added. The
mixture was then stirred at room temperature for 2 h and then
left to stand for 2 h. The solid was filtered, washed with water
and ethanol, and dried under vacuum. Yield: 45%.
C22H14ClMnN2O6·4.5H2O (573.60): calcd. C 46.06, H 4.00, N 4.88;
found C 46.09, H 4.30, N 5.20.
SED-H2–Cu: The green solid was synthesized similarly to above
starting from Cu(OAc)2·H2O. Yield: 50%. C18H14CuN2O6·1.5H2O
(444.91): calcd. C 48.59, H 3.82, N 6.29; found C 48.60, H 3.74, N
7.01.
SED-H2–Zn: The yellow solid was synthesized similarly to above
starting from Zn(OAc)2·H2O. Yield: 45%. C18H14N2O6Zn·1.8DMF
(565.28): calcd. C 49.72, H 4.74, N 9.42; found C 49.98, H 4.51, N
9.87.
SBD-H2–AlCl: Al(Et)2Cl (670 μL; 1.30 mmol) was added under ar-
gon to an ethanolic suspension (30 mL) of SBD-H2 (0.41 g,
0.99 mmol). The solution became translucent after 2 h of stirring
at room temperature under argon. The volume of the mixture was
reduced to 1/4 by concentration under reduced pressure. The com-
plex precipitated upon the addition of diethyl ether, collected by
filtration, washed with diethyl ether, and dried under vacuum.
Yield: 95%. C22H14AlClN2O6·5.4H2O (561.87): calcd. C 46.03, H
4.41, N 4.98; found C 47.01, H 4.47, N 5.06.
SED-H2–Ni: SED-H2 (0.18 g, 0.48 mmol) was dissolved in a mix-
ture of water (30 mL) with a few drops of NaOH. An aqueous
solution (20 mL) of Ni(OAc)2·4H2O (0.14 g, 0.54 mmol) was
then added dropwise under vigorous stirring. After stirring at
room temperature for 30 min, an orange precipitate was filtered,
washed with water, and dried under vacuum. Yield: 45%.
C18H14N2NiO6·1.9H2O (446.67): calcd. C 48.40, H 3.98, N 6.27;
found C 48.41, H 4.34, N 7.09.
SBD-H2–Co: Co(OAc)2·4H2O (105 mg, 0.42 mmol) dissolved in
DMF (40 mL) was added dropwise to a solution of SBD-H2
(0.176 g, 0.42 mmol) in DMF (40 mL). After 2 h of stirring at room
temperature, methanol (100 mL) was added, and the precipitate
was collected by filtration, washed with methanol, and dried under
vacuum. Yield: 77%. C22H14CoN2O6·0.9DMF·4.3H2O (604.89):
calcd. C 49.04, H 4.07, N 6.71; found C 49.11, H 3.64, N 6.74.
SED-H2–MnCl: Mn(OAc)2·4H2O (0.15 g, 0.62 mmol) dissolved in
methanol (10 mL) was added to a suspension of SED-H2 (0.22 g,
0.62 mmol) in methanol (50 mL). The color changed from yellow
to greenish. After 4 h under reflux, the mixture was cooled to ambi-
ent temperature, and a saturated aqueous solution of LiCl (3 mL)
was added. A brownish-green solid was filtered, washed with water
and methanol, and dried under vacuum. Yield: 64%.
C18H14N2O6MnCl·0.5H2O (454.10): calcd. C 47.6, H 3.32, N 6.17;
found C 47.58, H 3.95, N 6.44.
Synthesis of the Hybrid Materials M–SED–MЈ (M = Cu, Co; MЈ
= Co, Cu, Zn, Ni, “MnCl”).
Co–SED–Cu: SED-H2–Cu (0.21 g, 0.47 mmol) was suspended in
water (35 mL) and solubilized upon adjustment of the pH to 8 by
addition of 0.2 m NaOH. Then [Co2(OH)3(DS0)] (0.20 g,
0.48 mmol) was dispersed into the solution under an inert gas, and
ethanol (35 mL) was added. The mixture was then stirred under
argon at 80 °C for 5 h. After cooling to room temperature, a light-
blue powder was isolated by filtration, washed with water and eth-
SED-H2–FeCl: Anhydrous FeCl3 (0.27 g, 1.68 mmol) dissolved in
ethanol (35 mL) was added dropwise to a suspension of SED-H2
(0.62 g, 1.68 mmol) in ethanol (80 mL) in the presence of triethyl-
amine (467 μL) under an inert gas. The color of the solution
changed from yellow to purple-red. After heating at reflux for 2 h,
the solution was cooled to ambient temperature, and its volume
anol, and dried under vacuum. Yield: 92%. Co2(OH)3.2
-
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S. Eyele-Mezui, E. Delahaye, G. Rogez, P. Rabu
(C18H12N2O6Cu)0.4·2.8H2O (392.70): calcd. C 22.02, H 3.56, N Co–(S,S)-SCD–MnCl: The procedure was identical to that above,
FULL PAPER
2.85, Cu 6.47, Co 30.04; found C 22.10, H 3.48, N 2.89, Cu 6.21,
Co 30.20.
starting from (S,S)-SCD-K2–MnCl. Yield: 60%. Co2(OH)3.40-
(C22H18N2O6MnCl)0.30·6H2O (432.81): calcd. C 18.32, H 4.84, N
1.94, Co 27.23, Mn 3.81; found C 18.77, H 4.03, N 1.93, Co 27.31,
Mn 3.85.
Co–SED–Ni: The title compound was obtained according to a pro-
ceduresimilar tothatusedfor Co–SED–Cu.Yield: 80%.Co2(OH)3.2
-
(C18H12N2O6Ni)0.4·2.9H2O (389.12): calcd. C 22.22, H 3.55, N
2.87, Ni 6.01, Co 30.32; found C 22.31, H 3.57, N 2.87, Ni 5.46,
Co 30.59.
Co–(R,R)-SCD–Co: The procedure was identical to that above,
starting from (R,R)-SCD-K2–Co. Yield: 50%. Co2(OH)3.12
-
(C22H18N2O6Co)0.44·4.5H2O (456.73): calcd. C 25.46, H 4.42, N
2.70, Co 31.48; found C 25.74, H 4.17, N 2.50, Co 30.97.
Co–SED–Co: The title compound was obtained according to a pro-
ceduresimilar tothatusedfor Co–SED–Cu.Yield: 80%.Co2(OH)2.6
-
Co–(S,S)-SCD–Co: The procedure was identical to that above,
(C18H12N2O6Co)0.7·6.4H2O (565.23): calcd. C 26.77, H 4.24, N starting from (S,S)-SCD–K2–Co. Yield: 50%. Co2(OH)3.58
3.49, Co 28.15; found C 26.83, H 3.85, N 3.43, Co 28.23. (C22H18N2O6Co)0.21·4H2O (348.52): calcd. C 15.92, H 4.44, N 1.69,
Co 37.37; found C 16.09, H 4.26, N 1.58, Co 36.84.
-
Co–SED–MnCl: The title compound was obtained according to a
procedure similar to that used for Co–SED–Cu. Yield: 71%. Cu–(R,R)-SCD–MnCl: The complex (R,R)-SCD-K2–MnCl (0.32 g,
Co2(OH)2.44(C18H12N2O6MnCl)0.78·7H2O (630.71): calcd. C 26.73, 0.5 mmol) was suspended in water (50 mL). The pH of the solution
H 4.12, N 3.46, Mn 6.79, Co 18.69; found C 27.47, H 3.97, N 3.38,
Mn 6.46, Co 18.35.
was adjusted to 8 by using 0.2 m NaOH. Then [Cu2(OH)3(DS)]
(0.22 g, 0.48 mmol) was dispersed into the solution under an inert
gas, and ethanol (50 mL) was added. The mixture was then stirred
under argon at 80 °C for 24 h. After cooling to room temperature,
a brown powder was isolated by filtration, washed with water and
Cu–SED–Cu: SED-H2–Cu (0.21 g, 0.47 mmol) was suspended in
water (35 mL) and solubilized upon adjustment of the pH to 8 by
addition of 0.2 m NaOH. Then [Cu2(OH)3(DS)] (0.22 g, 0.48 mmol)
was dispersed into the solution under an inert gas, and ethanol
(35 mL) was added. The mixture was stirred under argon at 80 °C
for 2 h. A light-blue powder was isolated by filtration, washed with
water and ethanol, and dried under vacuum. Yield: 76%. Cu2(OH)3-
ethanol, and dried under vacuum. Yield: 60%. Cu2(OH)2.26
-
(C22H18N2O6MnCl)0.87·3H2O (651.77): calcd. C 35.27, H 3.70, N
3.74, Cu 19.49, Mn 7.33; found C 35.22, H 4.07, N 3.53, Cu 19.44,
Mn 7.33.
(C18H12N2O6Cu)0.5·3.2H2O (465.48): calcd. C 25.08, H 3.39, N Cu–(S,S)-SCD–MnCl: The procedure was identical to that above,
3.24, Cu 34.13; found C 25.14, H 3.40, N 2.94, Cu 34.13.
starting from (S,S)-SCD-K2–MnCl. Yield: 60%. Cu2(OH)3.16-
(C22H18N2O6MnCl)0.42·4.3H2O (466.95): calcd. C 23.77, H 4.17, N
2.52, Cu 27.22, Mn 4.94; found C 23.92, H 3.97, N 2.77, Cu 27.12,
Mn 4.86.
Cu–SED–Ni: The title compound was obtained according to a pro-
ceduresimilartothatusedforCu–SED–Cu.Yield:76%.Cu2(OH)3.24
-
(C18H12N2O6Ni)0.38·1.1H2O (365.46): calcd. C 22.72, H 2.82, N
2.94, Ni 6.10, Cu 35.63; found C 22.83, H 2.99, N 2.86, Ni 5.42,
Cu 35.63.
Cu–(R,R)-SCD–Co: The procedure was identical to that above,
starting from (R,R)-SCD-K2–Co. Yield: 53%. Cu2(OH)3.24
-
(C22H18N2O6Co)0.30(DS)0.16·2.6H2O (411.09):calcd. C 24.89, H
4.37, N 2.04, Cu 30.92, Co 4.30; found C 25.04, H 3.77, N 2.37,
Cu 30.97, Co 3.54.
Cu–SED–Co: The title compound was obtained according to a pro-
ceduresimilartothatusedforCu–SED–Cu.Yield:66%.Cu2(OH)2.24
-
(C18H12N2O6Co)0.88·4.7H2O (611.43): calcd. C 31.10, H 3.63, N
4.03, Co 8.49, Cu 20.78; found C 31.09, H 3.90, N 4.10, Co 8.12,
Cu 20.78.
Cu–(S,S)-SCD–Co: The procedure was identical to that above,
starting from (S,S)-SCD-K2–Co. Yield: 45%. Cu2(OH)3.10
-
(C22H18N2O6Co)0.45·3.2H2O (446.86): calcd. C 26.61, H 3.97, N
2.82, Cu 28.44, Co 5.93; found C 26.66, H 3.90, N 2.41, Cu 28.37,
Co 6.16.
Cu–SED–MnCl: The title compound was obtained according to a
procedure similar to that used for Cu–SED–Cu. Yield: 66%.
Cu2(OH)2.72(C18H12N2O6MnCl)0.64·3H2O (510.59): calcd. C 27.10,
H 3.24, N 3.51, Mn 6.88, Cu 24.87; found C 27.93, H 3.58, N 4.02,
Mn 6.19, Cu 25.12.
Synthesis of the Hybrid Materials M–SBD–MЈ (M = Co, Cu; MЈ
= Mn, Co, “Al-Cl”)
Cu–SED–Zn: The title compound was obtained according to a pro-
Co–SBD–AlCl: The complex SBD-H2–AlCl (0.23 g, 0.5 mmol) was
suspended in water (35 mL). The pH of the solution was adjusted
to 8 by using 0.2 m NaOH. Then [Co2(OH)3(DS0)] (0.21 g,
0.48 mmol) was dispersed into the solution under an inert gas, and
ethanol (35 mL) was added. The mixture was then stirred under
argon at 80 °C for 15 h. After cooling to room temperature, an
orange powder was isolated by filtration, washed with water and
cedure similar to that used for Cu–SED–Cu. Yield: 66%. Cu1.32
Zn0.68(OH)2.72(C18H12N2O6Zn)0.64·3.4H2O (501.63): calcd.
-
C
27.58, H 3.42, N 3.57, Zn 17.21, Cu 16.72; found C 27.52, H 3.32,
N 4.12, Zn 17.19, Cu 16.73.
Synthesis of the Hybrid Materials M–SCD–MЈ (M = Co, Cu; MЈ
= Mn, Co)
ethanol, and dried under vacuum. Yield: 48%. Co2(OH)2.94
-
Co–(R,R)-SCD–MnCl: The complex (R,R)-SCD-K2–MnCl (0.32 g,
0.5 mmol) was suspended in water (35 mL). The pH of the solution
was adjusted to 8 by using 0.2 m NaOH. Then [Co2(OH)3(DS0)]
(0.20 g, 0.48 mmol) was dispersed into the solution under an inert
gas, and ethanol (35 mL) was added. The mixture was then stirred
under argon at 80 °C for 5 h. After cooling to room temperature,
a brown powder was isolated by filtration, washed with water and
(C22H12N2O6AlCl)0.53·4.5H2O (494.20): calcd. C 28.34, H 3.73, N
3.00, Al 2.89, Co 23.84; found C 27.91, H 4.32, N 3.63, Al 2.89,
Co 23.89.
Co–SBD–Co: The procedure was identical to that above, starting
from SBD-H2–Co. Yield: 50%. Co2(OH)2.84(C22H12N2O6Co)0.58
·
9H2O (594.67): calcd. C 25.77, H 4.71, N 2.73, Co 25.57; found C
25.85, H 3.69, N 2.54, Co 26.24.
ethanol, and dried under vacuum. Yield: 60%. Co2(OH)3.26
-
(C22H18N2O6MnCl)0.37·3.5H2O (420.16): calcd. C 23.27, H 4.06, N
2.47, Co 28.05, Mn 4.84; found C 23.83, H 4.36, N 1.98, Co 28.19,
Mn 4.59.
Co–SBD–MnCl: The procedure was identical to that above,
starting from SBD-H2–MnCl. Yield: 50%. Co2(OH)3.08
-
(C22H12N2O6MnCl)0.46·3.6H2O (460.83): calcd. C 26.38, H 3.46, N
12
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Functional Hybrid Materials
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0.48 mmol) was dispersed into the solution under an inert gas, and
ethanol (50 mL) was added. The mixture was then stirred under
argon at 80 °C for 15 h. After cooling to room temperature, a
brown powder was isolated by filtration, washed with water and
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(C22H12N2O6MnCl)0.67·2.6H2O (547.96) calcd. C 32.31, H 2.92, N
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Supporting Information (see footnote on the first page of this arti-
cle): FTIR spectra and list of absorption bands for all compounds,
solid-state OCD spectra of (R,R)-SCD–MnCl and (S,S)-SCD–
MnCl, magnetic measurements.
Acknowledgments
We thank the Centre National de la Recherche Scientifique
(CNRS), the Université de Strasbourg, and the Agence Nationale
de la Recherche (ANR contract 06-JCJC-0008 and 2010-BLAN-
913-01 C-BLUE) for funding. S. E.-M. thanks the French Ministry
for Education and Research for his Ph. D. grant. The authors
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Job/Unit: I20695
/KAP1
Date: 06-09-12 09:55:01
Pages: 15
Functional Hybrid Materials
Functionalized Layered Hybrids
New hybrid layered simple hydroxides have
been obtained by the functionalization of
cobalt and copper hydroxides by carboxy-
salen-type complexes.
S. Eyele-Mezui, E. Delahaye, G. Rogez,*
P. Rabu* ......................................... 1–15
Functional Hybrid Materials Based on
Layered Simple Hydroxide Hosts and Di-
carboxylate Schiff Base Metal Complex
Guests
Keywords: Hybrid materials / Layered com-
pounds / Schiff bases / Magnetic proper-
ties / Hydroxides
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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