[30]metallacrown-10 compounds: [mn(c14h9n2o3) (ch3oh) ] 10·5ch2cl2· 16 ch3oh·h2o and [fe(c14h9n2o3) (ch3ch) ] 10·3ch2cl2· 12.5 Ch3oh·5h2o

Article abstract of DOI:10.1002/1521-3773(20010316)40:6<1084::AID-ANIE10840>3.0.CO;2-U

A plauar decanuclear 30-membered core ring is present in the new manganese (see picture) and iron [30]azametallacrown-10 compounds. These compounds were prepared by using the pentadentate ligand N-phenylsalicylhydrazidate, and the metal atoms in each ring adopt a propeller configuration and have alternating Λ/Δ stereochemistries.

Full text of DOI:10.1002/1521-3773(20010316)40:6<1084::AID-ANIE10840>3.0.CO;2-U

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[
11] C. J. Hawker, J. M. J. Fr e chet, J. Am. Chem. Soc. 1990, 112, 7638 ±
647.
Therefore, there has been considerable interest in metal-
lacrown chemistry owing to its potential applications in
chemically modified electrodes, anion-selective separation
agents, liquid-crystal precursors, and magnetic materials.[
7
[
12] Kaifer and co-workers have reported dendritic structures in which a
ferrocene or dansyl group is located ªoff-centerº within Newkome-
type aliphatic amide dendrimers through which they anticipate
inducing directional properties. C. M. Cardona, T. D. McCarley,
A. E. Kaifer, J. Org. Chem. 2000, 65, 1857 ± 1864; C. M. Cardona, J.
Avarez, A. E. Kaifer, T. D. McCarley, S. Pandey, G. A. Baker, N. J.
Banzangi, F. V. Bright, J. Am. Chem. Soc. 2000, 122, 6139 ± 6144.
13] D. K. Smith, F. Diederich, Chem. Commun. 1998, 2501 ± 2502; D. J.
Pesak, J. S. Moore, T. E. Wheat, Macromolecules 1997, 30, 6467 ± 6482.
14] Solutions of metal complexes for ESI-MS were prepared by adding
excess dendrimer to the required metal salt.
3]
Salicylhydroxamic acid (H shi) was used as the template
3
ligand in the synthesis of the early metallacrowns. Many
examples of this kind of metallacrown are known, for
[
3, 4]
[1, 2, 5±8]
example, [9]metallacrowns-3,
[12]metallacrowns-4,
[
[
[
and [15]metallacrowns-5,[ which have a [M-N-O]n repeat
9]
unit that forms a cyclic structure. Several compounds with the
[10]
metallacrown structure type have been developed. Recent-
1
15] The large shift in the pyridyl signals in the H NMR spectrum upon
ly, an [18]metallacrown-6 using N-formylsalicylhydrazide
3 2 2 2
addition of zinc(ii) salts to CD OD, CD Cl , and D O solutions of the
[11]
(
H fshz) as a ligand was reported.
3
This metallacrown is
dendritic ligands suggests that the metal ion binds to the tripodal
nitrogen-donor core and does not interact with the oxygen-donor
atoms of the polyether chain.
the second kind of metallacrown with a [M-N-N] repeating
n
unit in which nitrogen atoms replace all the oxygen atoms in
the cyclic structure.
Although some [9]metallacrowns-3, [12]metallacrowns-4,
[15]metallacrowns-5, and an [18]metallacrown-6 are known,
there has yet been no report of any [30]metallacrown-10.
[
16] The titrations were undertaken in 95% CD
zinc(ii) perchlorate salt is not soluble in neat CD
17] The chemical shifts of the protons on trispyridyl ligands are quite
2
Cl
2
/5% CD
3
OD since the
2
Cl
2
.
[
n‡
n‡
different in [ML] and [ML
affected; see, for example: R. T. Jonas, T. D. P. Stack, Inorg. Chem.
998, 37, 6615 ± 6629, and refs therein.
2
]
environments, with H6 being most
1
3�
Taking the limitations of metallacrowns based solely on shi
and fshz3 templates into account, we have greatly expanded
the types of precursor ligands with the intention of modifying
the ring size, as well as the electronic, magnetic, and other
physical properties of the metallacrowns. We found that the
choice of ligand plays an important role in preparing new
metallacrowns with high nuclear number, such as the title
�
[
30]Metallacrown-10 Compounds:
[30]metallacrowns-10. Herein we provide a new potential
[
Mn(C H N O )(CH OH)] ´ 5CH Cl ´
14
9
2
3
3
10
2
2
pentadentate ligand N-phenylsalicylhydrazidate (1) (H bzshz,
3
1
6CH OH ´ H O and
3
2
Scheme 1a) and the first two [30]metallacrowns-10, 2 and 3.
[
1
Fe(C H N O )(CH OH)] ´ 3CH Cl ´
14
9
2
3
3
10
2
2
2.5CH OH ´ 5H O**
3
2
Shi-Xiong Liu,* Shen Lin, Bi-Zhou Lin, Chi-Chang Lin,
and Jian-Quan Huang
Metallacrowns are a new class of multinuclear clusters that
are analogous to crown ethers in both structure and func-
[
1, 2]
tion.
One may substitute heteroatoms such as transition
metals and nitrogen atoms for the methylene carbon atoms of
the parent crown ether complexes to form metallacrowns.
Scheme 1. Ligand H
M ˆ Mn, Fe) (b).
3
bzshz (a) and basic biding sites in compounds 2 and 3
(
[
*] Prof. S.-X. Liu, Dr. S. Lin, Dr. B.-Z. Lin, C.-C. Lin, J.-Q. Huang
Department of Chemistry, Fuzhou University
Fuzhou 350002 (P. R. China)
The two title [30]metallacrowns-10 are also the second kind of
metallacrown with a [M�N�N] repeating unit, which may be
Fax : (‡86)-591-3729860
n
more appropriately called an azametallacrown.[
12]
E-mail: sxliu@fzu.edu.cn
Prof. S.-X. Liu, C.-C. Lin, J.-Q. Huang
Other address:
[Mn(C14
H
9
N
2
O
3
)(CH
3
OH)]10 ´ 5CH
2
Cl
2
´ 16CH
3
OH ´ H
2
O
2
State Key Laboratory of Structural Chemistry
Fujian Institute of Research on the Structure of Matter
The Chinese Academy of Sciences, Fuzhou 350002, (P. R. China)
Dr. S. Lin
[
Fe(C14
H
9
N
2
O
3
)(CH OH)]10 ´ 3CH
3
2
Cl
2
´ 12.5CH
3
OH ´ 5H
2
O
3
Single-crystal X-ray analysis of compound 2 (Figure 1)
Other address:
Department of Chemistry, Fujian Normal University
Fuzhou 350007 (P. R. China)
showed that there is a planar decanuclear 30-membered ring
in the manganese metallacrown core. The 30-membered core
ring exhibits crystallographic centrosymmetry and is a [Mn-N-
N]10 ring with neighboring Mn ´´´ Mn interatomic distances of
Dr. B.-Z. Lin
Other address:
Institute of Material Physical Chemistry, Huaqiao University
Quanzhou, Fujian 362011 (P. R. China)
4.906(1) ± 4.986(2) Š. The size of the cavity in the 30-
membered ring, measured between the opposite carbon
atoms (less 1.57 Š for the van der Waals radii of carbon) is
6.80, 7.61, 6.39, 7.48, and 7.23 for C(13) ± C(13a), C(26) ±
[
**] We are grateful for financial support from the National Natural
Science Foundation of China (No. 29771007) and the Natural Science
Foundation of Fujian Province, China.
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Figure 1. Perspective view of 2 (solvent molecules and all hydrogen atoms
have been omitted for clarity). Selected bond lengths [Š] and angles [8]:
Mn1-O1 1.878(5), Mn1-O3 1.888(5), Mn1-O6 1.969(5), Mn1-N1 1.959(6),
Mn1-O4 2.267(6), Mn1-N4 2.350(6); O1-Mn1-O3 170.1(2), O3-Mn1-N1
Figure 2. Perspective view of 3 (solvent molecules and all hydrogen atoms
have been omitted for clarity). Selected bond lengths [Š] and angles [8]:
Fe1-O1 1.936(8), Fe1-O3 2.012(8), Fe1-O6 1.984(8), Fe1-N1 2.073(9), Fe1-
O4 2.142(9), Fe1-N4 2.183(9); O1-Fe1-O3 161.6(3), O3-Fe1-N1 75.6(3), O3-
Fe1-O6 96.2(3), O1-Fe1-O4 91.1(4), N1-Fe1-O4 86.2(3), O1-Fe1-N4 90.4
7
9.7(2), O3-Mn1-O6 92.0(2), O1-Mn1-O4 90.7(2), N1-Mn1-O4 89.1(2), O1-
Mn1-N4 88.7(2), N1-Mn1-N4 115.1(2), O4-Mn1-N4 155.9(2), O1-Mn1-N1
0.9(2), O1-Mn1-O6 97.7(2), N1-Mn1-O6 168.8(2), O3-Mn1-O4 92.2(2),
(
3), N1-Fe1-N4 118.4(4), O4-Fe1-N4 155.3(4), O1-Fe1-N1 86.3(3), O1-Fe1-
9
O6 102.2(4), N1-Fe1-O6 163.5(3), O3-Fe1-O4 91.1(4), O6-Fe1-O4 79.6(3),
O3-Fe1-N4 95.2(3), O6-Fe1-N4 76.0(3); average neighbor Fe ´´´ Fe distance
O6-Mn1-O4 83.7(2), O3-Mn1-N4 92.5(2), O6-Mn1-N4 72.5(2); average
neighbor Mn ´´´ Mn distance 4.953(2), average near-neighbor Mn ´´´ Mn
distance 9.274(2); Mn ´´´ Mn ´´´ Mn 137.52 ± 139.50.
4
1
.946(2), average near-neighbor Fe ´´´ Fe distance 9.315(2); Fe ´´´ Fe ´´´ Fe
38.92 ± 141.84.
C(26a), C(41) ± C(41a), C(55) ± C(55a), and C(71) ± C(71a),
respectively. The approximate dimensions of the oval-shaped
cavity are approximately 6.39 Š in diameter at the entrance,
approximately 13.19 Š (less 1.37 Š for the van der Waals radii
of the manganese atom) at its largest diameter at the center of
the cavity, and approximately 3.79 Š in depth.
5.70 Š in diameter at the entrance, approximately 13.67 Š
(less 1.24 Š for the van der Waals radii of the iron atom) at its
largest diameter at the center of the cavity, and approximately
4.16 Š in depth.
All the iron atoms of the ring adopt a distorted octahedron
coordination geometry of the FeN O type. Compared with
All manganese atoms in compound 2 (Figure 1) are in a
distorted octahedral MnN O environment. The deprotonated
2
4
the MnN O octahedron, there is no Jahn ± Teller distortion in
2
4
2
4
ligand bzshz3 acts as a multidentate ligand: one phenolate
oxygen atom, one carbonyl oxygen atom, and one hydrazide
nitrogen atom in the ligand are bound to each manganese
atom, whereas the other carbonyl oxygen atom and the other
hydrazide nitrogen atom in the ligand are chelated to an
adjacent manganese atom. Therefore, the ligand induces the
stereochemistry of the manganese(iii) ions into a propeller
configuration owing to the meridianal coordination of the O1,
N1, and O3 atoms of the ligand to the metal ion. The average
axial manganese�oxygen/nitrogen distance of 2.310 Š in
�
the FeN O octahedron of compound 3, owing to the d high-
5
2
4
spin electronic configuration of the iron(iii) ion.
[3, 4]
Several [9]metallacrown-3 compounds
and a [15]metal-
lacrown-5[ have the metal centers of the ring in a propeller
configuration and with the same chiralities. The manganese
and iron atoms in the [30]azametallacrown-10 compounds 2
and 3 exhibit a propeller configuration; however, the chir-
alities of the ten mamganese/iron atoms in the two com-
pounds alternate between the L and D forms.[ In each
azametallacrown, five methanol groups coordinated to the
metal centers with L configuration are found on one face of
the azametallacrown, and the remaining five methanol groups
coordinated to the other metal centers with D configuration
are found on the other face of the azametallacrown. The two
faces of each azametallacrown have opposite chiralities.
The planar decanuclear structures in the [30]azametalla-
crowns-10 2 and 3 are quite different from the planar
hexanuclear structures in several [18]metallacrowns-6.[
The average M ´´´ M ´´´ M interatomic angles in the 30-
membered core ring of 2 and 3 are 138.878 and 140.678,
respectively. These values are close to the interior angle of
1448 in an n-decagon. However, the average M ´´´ M ´´´ M
9b]
13]
compound 2 is approximately 0.386 Š longer than the average
base Mn�O/N distance of 1.924 Š. This typical Jahn ± Teller
elongation along the z axis of the manganese(iii) ion was also
[
10]
observed in some manganese(iii) compounds.
All the
manganese ions in the ring of the title compound 2 adopt a
propeller configuration, despite the Jahn ± Teller distortion of
4
high-spin d manganese(iii) ions.
14]
The crystal structure of compound 3 (Figure 2) is similar to
that of compound 2 (Figure 1). The neighboring Fe ´´´ Fe
interatomic distances in the 30-membered ring with an [Fe-N-
N]10 repeat unit are 4.923(2) ± 4.966(2) Š. The approximate
dimensions of the oval-shaped cavity are approximately
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angles in the [18]metallacrowns-6 are 116.89(2)8 for
from the absolute values of J and J . The antiferromagnetic
1 2
[
Mn (C H N O S) (CH OH) ] ´ 11.5CH OH, and 118.16(4)8
nature of the interactions can be understood in terms of an
overlap, through the bridging group, between the singly
occupied metal d orbitals. Furthermore, Mn3 in an elongated
octahedral geometry exhibits magnetic anisotropy due to the
zero-field splitting (ZFS), but the system is too complex to
include the ZFS in magnetic analysis.
In summary, the manganese(iii) and iron(iii) [30]azametal-
lacrown-10 compounds 2 and 3 expand the ring size of known
metallacrown clusters from [9]metallacrown-3 to a 30-mem-
bered ring system. All the metal atoms in the rings of 2 and 3
adopt a propeller configuration, and have alternating L/D
stereochemistries. The manganese azametallacrown mole-
cules show large magnetic moments and have a remarkable
toroid-like shape with a relatively large internal cavity. Hence
it is possible that such molecules may act as a
scaffold for the formation of supermolecules by
guest binding within the cavity. It may also suggest
a new approach for developing magnetic materi-
als.
6
8
6
3
2
6
3
6
3
[
14]
for [Fe (C H N O S) (CH OH) ] ´ 12CH OH ´ 2H O, which
6
8
6
3
2
6
3
6
3
2
‡
are close to the ideal internal angle of 1208 in an n-hexagon.
The change in the ring size between the [30]metallacrowns-10
and the [18]metallacrowns-6 is probably caused by the steric
interactions between the bridging multidentate ligands in the
different metallacrowns.
The magnetic behavior of 2 is illustrated in Figure 3. The
molar effective magnetic moment (m ) decreases slightly with
decreasing temperature from 14.73 m at 275 K to 13.32 m at
6
4
the sum expected for ten discrete paramagnetic systems with
S ˆ 2 (meff ˆ 15.18 m ). This is characteristic of antiferromag-
eff
B
B
0 K. Below 60 K, meff decreases rapidly and reaches 4.38 m at
B
K. Even at 275 K, the meff value is smaller than the value of
B
Experimental Section
1
: Benzoyl chloride (5.55 g, 39.5 mmol) was added to a
solution of sodium benzoate (5.688 g, 39.5 mmol) in chloro-
form (60 mL) at 58C. The reaction mixture was slowly
warmed to 228C, stirred for 2 h, and then filtered. Salicylhy-
drazide (5.00 g, 32.9 mmol) was added to the filtrate to give a
white suspension, which was collected and rinsed with
chloroform and diethyl ether. Yield: 8.200 g, 95.0%, m.p.
2
558C.
2
2
: A mixture of [Mn(acetylacetonate) ] (35 mg, 0.1 mmol) in
methanol (15mL) and N-phenylsalicylhydrazidate (25 mg,
0.1 mmol) in chloroform (15 mL) was stirred for 15 min. The
resulting dark brown solution was filtered. After standing for
six days, dark brown rectangular crystals were obtained from
the filtrate. Compound 2 is air-sensitive. Elemental analysis:
�
1
Figure 3. The effective magnetic moment (meff) and the inverse susceptibility c
m
data as a
function of temperature for 2. Open points represent observed results, and solid lines for
�
1
c
m
and meff represent the fitting curves based on the Curie ± Weiss law and on a simplified
exchange fit as described in the text, respectively.
C
2
171
H
206Cl10Mn10
N
20
O
57 (%): calcd: C 47.1, H 4.8, N 6.4, O
0.9; found: C 46.6, H 4.4, N 6.8, O 21.3.
: A mixture of Fe(OAc) (46.6 mg, 0.2 mmol) in methanol (15 mL) and N-
3
3
netic coupling, which is further suggested by a negative Weiss
phenylsalicylhydrazidate (51.4 mg, 0.2 mmol) in chloroform (15 mL) was
stirred for 15 min. The resulting dark violet-red solution was filtered. After
standing for seven days, black-brown rhombohedral crystals were sepa-
rated from the filtrate. Compound 3 is air-sensitive. Elemental analysis:
constant (q ˆ � 16.0(1) K) using the data within T> 63 K.
[
15]
Based on irreducible tensor operators with the Hamiltonian
operator given as H ˆ � SJ S S , one can get the energy of
ij
i j
C
165.5
H
196Cl
6
Fe10N
20
O
57.5 (%): calcd: C 47.8, H 4.8, N 6.7, O 22.1; found: C
8
56945 spin states arising from the coupling of the 10 S ˆ 2
4
7.2, H 4.4, N 7.1, O 22.5.
centers. Nevertheless, because of the different S values
ranging from 0 to 20, the dimensions of the Hamiltonian
matrices are too big for a true fitting procedure, even when
taking the inverse center symmetry into account. Therefore, a
simplified set of parameters for magnetic interactions were
tested to analyze the magnetic properties quantitatively.
Crystals of compounds 2 and 3 were mounted in a glass capillary with the
mother liquor to prevent the loss of the structural solvents during X-ray
diffraction data collection. The data were recorded on a Siemens Smart
CCD area detector diffractometer with graphite-monochromated MoKa
radiation (l ˆ 0.71073 Š), the scan mode being w. Programs used: Data
correction: SMART (Siemens, 1996), cell refinement: SAINT (Siemens,
1
996), and data reduction: SAINT (Siemens, 1996). The structures were
Exchanges propagated between the neighboring centers (J ),
1
solved by direct methods using SHELXS-86 and refined by full-matrix
least-squares calculations with SHELXL-97. All non-hydrogen atoms were
refined with anisotropic thermal parameters. The hydrogen atoms on the
benzene ring in 2 and 3 were located at calculated positions (C�H ˆ 0.93 Š)
and between the near-neighboring centers (J ) were consid-
2
ered. The distances between the paramagnetic centers in
other positions are greater than 12.749(2) Š. Consequently,
their interactions are weak and negligible. A least-squares fit
with isotropic displacement parameters set to 1.2 Ueq(C). Some of the other
hydrogen atoms in 2 were located at calculated positions and/or at the
positions found from a difference Fourier map. Crystallographic data
(excluding structure factors) for the structures reported in this paper have
been deposited with the Cambridge Crystallographic Data Centre as
supplementary publication nos. CCDC-148152 (2) and CCDC-148153 (3).
Copies of the data can be obtained free of charge on application to CCDC,
for all the data gives rise to the parameters J /k ˆ
1
�
1.275(2) K, J /k ˆ � 0.73(3) K, and the agreement factor
2
2
� 3
F ˆ S[(c � c ) /c ] ˆ 7.893  10 . The negative values of
obs
cald
obs
J denote antiferromagnetic coupling between the manga-
nese(iii) centers. As expected, the interactions between
neighboring centers dominate the others that are derived
1
2 Union Road, Cambridge CB21EZ, UK (fax: (‡44)1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk).
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Crystal data for 2 (C171
H
206Cl10Mn10
N
20
O
57): M
r
ˆ 4357.46, dark brown
Coordination Chemistry in the Solid: Study of
Å
crystal (0.35  0.40  0.55 mm), triclinic, space group P1, a ˆ 14.5331(2),
II
the Incorporation of Cu into Cyclam-
b ˆ 18.1704(1), c ˆ 21.3923(2) Š, a ˆ 76.545(1), b ˆ 74.220(1), g ˆ
3
� 3
8
6.025(1), Vˆ 5287.03(9) Š , Z ˆ 1, Tˆ 293(2) K,
1
calcd ˆ 1.369 gcm
,
Containing Hybrid Materials
�
1
F(000) ˆ 2248, m ˆ 0.782 mm
.
Of the 28654 reflections ((2q)max
ˆ
Geraud Dubois, Catherine Rey e , Robert J. P. Corriu,*
St e phane Brand eÁ s, Franck Denat, and Roger Guilard*
5
0.148), 18480 unique reflections were collected. From these, 9215
reflections with I > 2s(I) were used to solve the structure and were refined
on F 2 by full-matrix least-squares techniques (SHELXL-97). At conver-
2
gence, R
1
ˆ 0.0834 and the goodness-of-fit on F is 1.121. The maximum and
Nanostructured organic ± inorganic hybrid materials have
known a considerable expansion in the past decade,[
because they may provide unique combinations of properties
which cannot be obtained by other ways. Among the
possibilities offered by this class of solids, the preparation of
materials able to strongly chelate metal cations which could
remain chemically accessible seemed to us to be of great
interest. Indeed, such materials could be interesting to study
the coordination chemistry within the solid state as well as for
minimum residual peaks on the final difference Fourier map were 0.934 and
1±5]
�
3
�
0.879 eŠ , respectively.
Crystal data for 3 (C165.5
H
196Cl
6
Fe10N
20
O
57.5): M
r
ˆ 4156.62, black-brown
Å
crystal (0.34  0.35  0.72 mm), triclinic, space group P1, a ˆ 14.7040(4),
b ˆ 18.9081(5), c ˆ 21.0783(5) Š, a ˆ 71.201(1), b ˆ 77.076(1), g ˆ
3
� 3
8
4.757(1), Vˆ 5406.0(2) Š , Z ˆ 1, Tˆ 293(2) K,
1
calcd ˆ 1.277 gcm
,
�
1
F(000) ˆ 2151, m ˆ 0.800 mm . Of the 23991 reflections ((2q)max ˆ 47.108),
1
4784 unique reflections were collected. From these, 7372 reflections with
2
I > 2s(I) were used to solve the structure and were refined on F by full-
matrix least-squares techniques (SHELXL-97). At convergence, R
1
ˆ
2
[6]
[7]
0.0945 and the goodness-of-fit on F is 1.017. The maximum and minimum
their potential applications in catalysis, separations, optical
residual peaks on the final difference Fourier map were 0.893 and
[8]
devices, or magnetic properties for example. Such applica-
�
3
�
0.455 eŠ , respectively.
tions require the incorporation within the materials of a good
The magnetic susceptibility data were obtained by using a Quantum Design
PPMS 6000 magnetometer in the temperature range from 4 to 275 K at an
applied magnetic field of 10 KG; whereby the diamagnetic contributions
were estimated from Pascalꢁs constants.
chelating ligand. Saturated polyazamacrocycles and especially
9±11]
1
,4,8,11-tetraazacyclotetradecane[
(cyclam) having attract-
ed much attention because of their remarkable binding ability
towards transition and heavy metal cations, we set out to
prepare hybrid materials incorporating cyclam moieties by
using the sol ± gel process.
Received: August 28, 2000
Revised: November 27, 2000 [Z15711]
We have shown that nanostructured materials are kineti-
[
1] V. L. Pecoraro, A. J. Stemmler, B. R. Gibney, J. J. Bodwin, H. Wang,
cally controlled.[
3, 4, 12]
The texture of the solids is highly
J. W. Kampf, A. Barwinski, Progress in Inorganic Chemistry, Vol. 45
dependent on all the parameters able to modify the kinetics of
(Ed.: K. D. Karlin), Wiley, New York, 1997, pp. 83 ± 177.
[
13]
[13]
[
[
2] M. S. Lah, V. L. Pecoraro, J. Am. Chem. Soc. 1989, 111, 7258.
3] a) M. S. Lah, M. L. Kirk, W. Hatfield, V. L. Pecoraro, J. Chem. Soc.
Chem. Commun. 1989, 1606; b) M. S. Lah, V. L. Pecoraro, Comments
Inorg. Chem. 1990, 11, 59.
polycondensation (catalyst, concentration of the reagent,
solvent, temperature,
[13]
[13a]
[13]
and the organic spacer ). Fur-
thermore, the importance of the organic moiety in the
arrangement of solids obtained by the sol ± gel process was
[
[
[
[
[
4] B. R.Gibney, A. J. Stemmler, S. Pilotek, J. W. Kampf, V. L. Pecoraro,
displayed, giving rise to a possible short-range organiza-
Inorg. Chem. 1993, 32, 6008.
5] A. J. Stemmler, J. W. Kampf, V. L. Pecoraro, Inorg. Chem. 1995, 34,
tion.[
3, 4, 14, 15]
In this context, it seemed interesting to inves-
2271.
tigate the incorporation of metal salts into cyclam-contain-
ing hybrid materials by two routes: the hydrolysis and
polycondensation of metal salt/silylated cyclam derivatives
complexes (Scheme 1, route A) or by hydrolysis and
polycondensation of silylated cyclam derivatives followed by
the direct incorporation of metal salts into the xerogels
6] B. Kurzak, E. Farkas, T. Glowiak, H. Kozlowski, J. Chem. Soc. Dalton
Trans. 1991, 163.
7] B. R. Gibney, D. P. Kessissoglou, J. W. Kampf, V. L. Pecoraro, Inorg.
Chem. 1994, 33, 4840.
8] a) B. R. Gibney, H. Wang, J. W. Kampf, V. L. Pecoraro, Inorg. Chem.
1996, 35, 6184; b) J. A. Halfen, J. J. Bodwin, V. L. Pecoraro, Inorg.
Chem. 1998, 37, 5416.
(
Scheme 1, route B).
[
9] a) D. P. Kessissoglou, J. Kampf, V. L. Pecoraro, Polyhedron 1994, 13,
We have shown that the hydrolysis and polycondensation of
1379; b) A. J. Stemmler, A. Barwinski, M. J. Baldwin, V. Young, V. L.
II
II
Pecoraro, J. Am. Chem. Soc. 1996, 118, 11962; c) A. J. Stemmler, J. W.
Kampf, V. L. Pecoraro, Angew. Chem. 1996, 108, 3011; Angew. Chem.
Int. Ed. Engl. 1996, 35, 2841.
silylated cyclam Cu and Co complexes (route A, Scheme 1)
gives rise quantitatively to hybrid materials incorporating the
II
II
[16]
Cu and Co salts, thus the complexation of metal cations
survives the sol ± gel process. Herein we describe the direct
[
10] a) K. L. Taft, C. D. Delfs, G. C. Paraefthymiou, S. Foner, D. Gatteschi,
S. J. Lippard, J. Am. Chem. Soc. 1994, 116, 823; b) A. Caneschi, A.
Cornia, S. J. Lippard, Angew. Chem. 1995, 107, 511; Angew. Chem. Int.
Ed. Engl. 1995, 34, 467; c) S. P. Watton, P. Fuhrmann, L. E. Pence, A.
Caneschi, A. Cornia, G. L. Abbati, S. J. Lippard, Angew. Chem. 1997,
incorporation of CuCl into hybrid materials (route B). By
2
using X-ray fluorescence and ESR spectroscopy, we show that
the two routes of incorporation of the salts are not equivalent
109, 2917; Angew. Chem. Int. Ed. Engl. 1997, 36, 2774; d) A. Caneschi,
A. Cornia, A. C. Fabretti, D. Gatteschi, Angew. Chem. 1999, 111, 1372;
Angew. Chem. Int. Ed. Engl. 1999, 38, 1295.
11] B. Kwak, H. Rhee, S. Park, M. S. Lah, Inorg. Chem. 1998, 37, 3599.
12] The authors are grateful for the suggestion from a referee.
13] The L and D forms are defined using a skew line convention for the
[
*] Prof. R. J. P. Corriu, Dr. G. Dubois, Prof. C. ReyeÂ
Universit e Montpellier II
[
[
[
3
4095 Montpellier Cedex 5 (France)
Fax : (‡33)467143852
compounds with a pseudo-C
2
axis as described in Inorg. Chem. 1970, 9,
E-mail: corriu@crit.univ-montp2.fr
1.
[
14] [Mn
CH
6
(C
8
H
6
N
3
O
2
S) ] ´ 11.5CH
6
(CH
3
OH)
6
3
OH and [Fe
6
(C
8
H
6
N
3
O
2
S)
6
´
Prof. R. Guilard, Dr. S. Brand eÁ s, Dr. F. Denat
UMR 5633 Universit e de Bourgogne
6 Boulevard Gabriel, 21100 Dijon (France)
Fax: (33)380396117
(
3
OH)
6
] ´ 12CH OH ´ 2H O were obtained by us, and their crystal
3
2
structures are different from the structures of 2 and 3. Details will be
reported elsewhere.
[
15] D. Gatteschi, L. Pardi, Gazz. Chim. Ital. 1993, 123, 231.
E-mail: limsag@u-bourgogne.fr
Angew. Chem. Int. Ed. 2001, 40, No. 6
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