Self-assembly and characterization of grid-type copper(I), silver(I), and zinc(II) complexes

Article abstract of DOI:10.1002/ejic.200500313

The reactions of ligand L, which comprises two bidentate binding units, with copper(I), silver(I), and zinc(II) lead to the self-assembly of the expected supramolecular architectures 1-3, respectively, of the [2 x 2] grid type, containing four ions in tet

Full text of DOI:10.1002/ejic.200500313

FULL PAPER
Self-Assembly and Characterization of Grid-Type Copper(
Zinc(II) Complexes
I
), Silver( ), and
I
Violetta Patroniak,*[a,b] Artur R. Stefankiewicz,[a,b] Jean-Marie Lehn,[b] and
Maciej Kubicki[a]
Dedicated to Professor Bogdan Marciniec on the occasion of his 65th birthday
Keywords: Copper / Silver / Zinc / Supramolecular chemistry / Self-assembly
The reactions of ligand L, which comprises two bidentate
binding units, with copper( ), silver( ), and zinc(II) lead to the
self-assembly of the expected supramolecular architectures
1–3, respectively, of the [2×2] grid type, containing four ions
in tetrahedral coordination sites. The grid-type structures are
assigned on the basis of the spectroscopic data in solution,
and confirmed in the solid state in the case of complex 2 by
X-ray crystallography.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
I
I
grids. Such compounds form supramolecular systems that
self-assemble into monolayer or bilayer crystalline films,
which are of potential interest for microelectronics and
nanotechnology.[38–41] Zinc is one of the most abundant
metals in the human body, and fluorescent imaging has
been proven to be the most suitable technique for its moni-
toring in vivo.[42,43]
One aim of our studies has been to explore further the
possibilities of the self-assembly of supramolecular struc-
tures, in particular multinuclear grids from N-heterocyclic
ligands. In this paper, we describe the synthesis and struc-
tural characterization of some polynuclear metal complexes
prepared from the tetradentate ligand L, which contains
pyridine and pyrimidine nitrogen donor atoms. The investi-
gation of the complexation of ligand L with metal ions of
preferred tetrahedral coordination geometry, such as CuI,
AgI, and ZnII, has revealed that the ligand is adequately
preorganised for the assembly of tetranuclear [2×2] grid
type complexes.
Introduction
Metal-directed self-assembly is a powerful synthetic
methodology for supramolecular architectures that may ex-
hibit novel physical and chemical properties with potential
applications in supramolecular engineering, nanotechnol-
ogy, biomedical inorganic chemistry, biological catalysis,
and in the area of sensors. A variety of architectural types
are known, such as, for example, inorganic double,[1–5] tri-
ple,[4,5] and quadruple[6] helicates, rotaxanes,[7–9] clus-
ters,[10–12] racks,[13] cages,[14–16] grids[17–28] etc., based on li-
gand design and on the application of suitable coordination
geometries for the assembly process. Among them, there is
an increasing interest in grid-shaped complexes based on
ligands containing oligopyridine-type groups and various
transition metal ions. These grids are thermodynamically
most stable when metal ions of tetrahedral coordination ge-
ometry are combined with a planar ligand containing bi-
dentate binding subunits.[17,18,29–40] The first [2×2] grid
type was obtained with copper() ions,[17] and copper() grid
complexes have recently attracted much attention because
of their well-defined supramolecular architectures and their
interesting properties, such as special optical,[35] mag-
netic,[36] and electrochemical features or the atypical geome-
try of the grid structure.[37] Silver() has also been used as
an assembling ion and, thanks to the flexibility of its coor-
dination sphere, has yielded sophisticated coordination
architectures such as [3×3][29] and [(2×5)2][6] multinuclear
Results and Discussion
Synthesis of Ligand L
Ligand L possesses two N,N bidentate binding subunits
for the complexation of ions with tetrahedral coordination
geometry. It contains heterocyclic pyrimidine and pyridine
units and was synthesised as outlined in Scheme 1.
2-Methyl-6-(trimethylstannyl)pyridine was obtained
from 2-bromo-6-methylpyridine by a halogen/lithium ex-
change protocol at low temperature in THF with n-butyl-
lithium, followed by quenching the pyridyllithium interme-
[a] Faculty of Chemistry, Adam Mickiewicz University,
Grunwaldzka 6, 60780 Poznan´, Poland
E-mail: violapat@amu.edu.pl
[b] ISIS, Université Louis Pasteur,
8, Allée Gaspard Monge, BP 70028, 67083 Strasbourg, France
4168
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200500313
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Grid-Type Copper(), Silver(), and Zinc() Complexes
FULL PAPER
Scheme 1. Reaction scheme for the synthesis of ligand L.
diate with ClSnMe3.[44,45] 4,6-Dichloro-2-phenylpyrimidine The bond-angle pattern is also typical, with distortions
was prepared by treatment of POCl3 with 2-phenylpyrimi- from the ideal (120°) caused by the presence of heteroatoms
dine-4,6-diol.[46] The twofold Stille-type[47] coupling reac- and substituents. In the crystal structure, the principal
tion of 2-methyl-6-(trimethylstannyl)pyridine with 4,6- intermolecular interaction is probably π-stacking between
dichloro-2-phenylpyrimidine in toluene using [Pd(PPh3)4] as neighbouring molecules (approximately along the [610] di-
a catalyst furnished L in 54% yield after workup. The struc- rection); the mean distance between the π systems is 3.44 Å.
ture of ligand L was confirmed by NMR spectroscopy, FAB
mass spectrometry, and elemental analysis. It was also
structurally characterized by X-ray crystallography (Fig-
ure 1).
Synthesis and Characterization of the Complexes
Multitopic ligands with N,N-type donor sets allow the
metal ion-directed assembly of coordination architectures.
Thus, ligand L leads to the generation of the [2×2] grid
architectures 1–3 with CuI, AgI, and ZnII, respectively
(Scheme 2).
The self-assembly of these complexes was achieved by
reaction of L in acetonitrile, at room temperature, with tet-
rakis(acetonitrile)copper() hexafluorophosphate or the sil-
ver() and zinc() triflates. The complexation reactions were
followed by ESI mass spectrometry and NMR spec-
troscopy.
1
The H NMR spectra of the complexes show strongly
shifted signals, as expected, and are strongly supportive of
the grid-type structures. The signals of the symmetrically
coordinated ligand in a single chemical and magnetic envi-
ronment are in agreement with this type of structure. Inter-
estingly, significant coordination-induced shifts of the sig-
nals are observed when the spectra of the complexes are
compared to those of the uncomplexed ligand L.
ESI mass spectrometry is a highly sensitive and accurate
analytical tool, which has been found to be particularly
suitable for the identification of large metallosupramolecu-
lar architectures in solution, in which multiply charged ions
are generated by sequential loss of counterions, resulting in
characteristic isotopic patterns in the spectrum. The ESI-
MS investigation of all complexes was performed with ace-
tonitrile solutions at approximately 10–4 . For example, the
Figure 1. Anisotropic-ellipsoid representation of molecule L to-
gether with the numbering scheme. The ellipsoids are drawn at the
50% probability level; hydrogen atoms are represented by spheres
of arbitrary radii.
Crystallographic Characterization of Ligand L
The crystal structure of the ligand molecule L shows that ESI mass spectrum of 2 shows peaks corresponding to mul-
it is approximately planar (Figure 1). The four constituent tiply charged species at m/z = 785 (80%, [AgL2]+), 447
rings are planar within the experimental error [maximum (100%, [Ag4L4]4+), 339 (45%, [L]+). These data confirm the
deviation from the least-squares plane is 0.012(3) Å], and presence of grid 2 in solution. The spectra of all the com-
the dihedral angles between their planes are small, up to plexes include signals for [ML2]n+, [M4L4]n+, and [L]+,
6.7(2)°. The mean values of aromatic Car–Car [1.373(9) Å], which means that significant dissociation of the grid com-
single Car–Car [1.489(6) Å], Car–Csp3 [1.506(4) Å], and Car– plexes to mononuclear species and ligand molecules occurs
N [1.340(4) Å] bond lengths are very close to typical values. in solution.
Eur. J. Inorg. Chem. 2005, 4168–4173
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V. Patroniak, A. R. Stefankiewicz, J.-M. Lehn, M. Kubicki
FULL PAPER
Scheme 2. Reaction scheme for the assembly of the [2×2] grid complexes 1–3.
Solid-State Molecular Structure of Complex 2
direction (atoms C2, C21, C24, and C5 lie at Wyckoff posi-
tions g).
Crystals of complex 2 were obtained by diffusion of di-
isopropyl ether into a solution of the complex in acetoni-
trile. The molecular structure of complex 2 was determined
by X-ray crystallography at both 291 K and 100 K. It shows
that it is of [2×2] grid-type (Figure 2), and is stable from
100 K to at least room temperature. We will discuss the low
temperature structure here, but this discussion is equally va-
lid for the structure determined at room temperature.
Due to its symmetry, the grid is of rhombic shape and
its size is within nanoscopic scale − the lengths of the diago-
nals are 1.18 and 1.92 nm. The formation of the grid causes
significant changes in the shape of the ligand molecule. The
free ligand molecule present in the crystal has a structure
similar to that determined for L, with a maximum value of
the dihedral angle between the least-squares of the aromatic
planes of 9.9°. In contrast, the molecule in the complex is
fairly folded. The dihedral angles between the planes of the
central ring and terminal rings are 13.0°, 22.6°, and 40.0°,
and the dihedral angles between the planes of the terminal
rings are as large as 56.9°.
The AgI ions show distorted tetrahedral coordination,
and the Ag···Ag distances are in the range 6.640–12.087 Å.
The Ag–N distances can be divided into two classes: shorter
[2.276(4) Å and 2.219(3) Å], to pyrimidine nitrogen atoms,
and longer [2.449(5) Å and 2.471(5) Å], to pyridine nitrogen
atoms. Selected bond lengths and angles are listed in
Table 1.
Table 1. Selected geometrical parameters of the [2×2] grid-type
complex 2.[a]
Figure 2. Anisotropic-ellipsoid representation of molecule 2 to-
gether with numbering scheme. The ellipsoids are drawn at the 50%
probability level; hydrogen atoms are represented by spheres of ar-
bitrary radii. The counterions, diisopropyl ether, and ligand mole-
cules have been omitted for clarity.
Ag1–N1A
2.449(5)
2.276(4)
2.219(3)
2.471(5)
1.387(14)
1.349(14)
150.4(2)
133.2(1)
70.7(1)
92.6(2)
164.3(2)
72.2(2)
114.9(2)
130.1(2)
Ag1–N61A
Ag2–N41A
Ag2–N3A
Ͻ(C–C)arϾ
Ͻ(C–N)arϾ
N61A–Ag1–N61Ai
The unit cell contains, besides the grid molecules, also
the free ligand, counterion (triflate), and disordered solvent N61A–Ag1–N1Ai
N1A–Ag1–N61A
(diisopropyl ether) molecules. The grid is highly symmetri-
N1A–Ag1–N1Ai
cal: two independent silver ions, which lie on two different
N41A–Ag2–N41Aii
twofold axes, occupy the special positions of the space
N3A–Ag2–N41A
N41A–Ag2–N3Aii
N3A–Ag2–N3Aii
group Ccca. One of them occupies the Wyckoff position e
(twofold axis along x), while the other occupies the Wyckoff
position f (twofold axis along y). Thus, the symmetry-inde-
pendent part of the grid contains two halves of silver ions
and one ligand, and the rest is produced by symmetry oper-
i
ii
[a] Symmetry codes: 1 – x, y, 1/2 – z; x, 1/2 – y, 1/2 – z.
The triflate anions are situated between the grid mole-
ations. The free ligand molecule occupies yet another spe- cules and are held there by relatively strong and linear C–
cial position, that on the third twofold axis along the z- H···O hydrogen bonds (Table 2, Figure 3). Approximately
4170
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Grid-Type Copper(), Silver(), and Zinc() Complexes
FULL PAPER
planar, free ligand molecules lie between the grids, and in- plexes, which were characterized in solution on the basis
1
teract with the aromatic rings by π-stacking interactions of ESI mass spectrometry and H NMR spectroscopy. The
(the distance between the mean planes of the rings is about molecular structure of the AgI complex 2 was also investi-
3.4 Å). This intercalation occurs between two different grid gated by X-ray crystallography, which confirmed that it in-
fragments; an analogous intra-grid intercalation of the free deed has a [2×2] grid-type architecture, with each metal ion
ligand is observed, for example, in the copper() biphenan- tetrahedrally coordinated by two N,N donors.
throline grid structure.[33] There is additional free space in
The present results detail a particularly facile and rapid
the crystal structure that is filled by disordered diisopropyl synthetic protocol for the preparation of [2×2] grid-type
ether solvent molecules.
coordination scaffolds with CuI, AgII, and ZnII. Related li-
gands and coordination arrays may be envisioned for the
generation of various metallosupramolecular architectures.
Table 2. Hydrogen bond data for 2 (low-temperature data).
D
H
A
D–H
[Å]
H···A
[Å]
D···A
[Å]
D–H···A
[°]
C461 H46C O3i
C65A H65A O2ii
C661 H66B O3ii
0.96
0.93
0.96
0.92
0.92
2.34
2.34
2.48
2.48
2.46
3.242(7)
3.275(7)
3.429(7)
3.380(6)
3.303(7)
157
176
172
168
153
Experimental Section
General: CH3CN was freshly distilled under argon over CaH2. 2-
Methyl-6-(trimethylstannyl)pyridine[44,45] and 4,6-dichloro-2-phen-
ylpyrimidine[46] were prepared according to the literature. The me-
tal salts were used without further purification as supplied by Ald-
rich. NMR spectroscopic data were recorded on a Varian Gemini
300 MHz spectrometer, and were calibrated against the residual
protonated solvent signal (CDCl3: δ = 7.24 ppm; CD3CN: δ =
1.94 ppm) and are given in ppm. Mass spectra were determined by
FAB+ using a ZAB-HF VG apparatus in a m-nitrobenzyl alcohol
matrix and a Waters Micromass ZQ spectrometer in acetonitrile.
The electronic absorption spectrum for ligand L in acetonitrile was
measured on a Shimadzu UV 2401 PC spectrometer, with λmax in
nm and ε (×104) in –1 cm–1. The luminescence spectrum for ligand
L in CH3CN was recorded using a Perkin–Elmer MPF-3 spectro-
fluorimeter. Microanalyses were obtained using a Perkin–Elmer
2400 CHN microanalyzer. Melting points were recorded on an
Electrothermal Digital melting point apparatus.
C5A H5A
O1
C43A H43A O1
i
ii
[a] Symmetry codes: 1 – x, y, 1/2 – z; x, 1/2 – y, 1/2 – z.
4,6-Bis(6-methylpyridin-2-yl)-2-phenylpyrimidine (L): 2-Methyl-6-
(trimethylstannyl)pyridine (2.0 g, 8 mmol) and degassed toluene
(25 mL) were added consecutively, by syringe, to a mixture of 4,6-
dichloro-2-phenylpyrimidine (0.6258 g, 3 mmol), [Pd(PPh3)4]
(0.10 g, 0.9 mmol), and LiCl (0.68 g, 16 mmol) under argon. The
reaction was refluxed and stirred at 120 °C for 24 h, and the toluene
evaporated in a water bath under reduced pressure. The residue was
then purified by column chromatography on alumina and eluted
with dichloromethane/n-hexane (4:6); yield: 0.50 g (54%). 1H NMR
(300 MHz, CDCl3): δ = 9.27 (s, 1 H, H-5), 8.72 (t, J = 7.9 Hz, 1
H, H-4ЈЈЈ), 8.50 (d, J = 7.6 Hz, 2 H, H-2ЈЈЈ,6ЈЈЈ), 7.79 (t, J = 7.6 Hz,
2 H, H-4Ј,4ЈЈ), 7.54 (m, J = 5.2 Hz, 4 H, H-3Ј,3ЈЈ,5Ј,5ЈЈ), 7.20 (t, J
= 7.9 Hz, 2 H, H-3ЈЈЈ,5ЈЈЈ), 2.66 (s, CH3) ppm. 13C NMR (DEPT,
75 MHz, CDCl3): δ = 164.4, 163.9, 158.4, 154.1, 138.0 (CH), 137.2
(CH), 130.6, 128.5 (CH), 128.4 (CH), 124.9 (CH), 119.0 (CH),
111.6 (CH), 24.6 (CH3). FAB-MS: m/z (%) = 339.2 (100) [L + H].
UV/Vis (CH3CN): λ = 233, 272.5, 281.5, 318 nm. Luminescence:
λex. = 298 nm, λem. = 356 nm. C22H18N4 (338.4): calcd. C 78.08, H
5.36, N 16.56; found C 77.99, H 5.33, N 16.42. M.p. 170 °C.
Figure 3. The content of the unit cell as seen approximately along
the a direction (z across, b down). Weak hydrogen bonds are drawn
as dashed lines.
Cu Complex 1: An equimolar mixture of [Cu(CH3CN)4]PF6
(11.0 mg, 30 µmol) and ligand L (10.0 mg, 30 µmol) in MeCN
(5 mL) was stirred at room temperature for 24 h. The solvent was
then evaporated under reduced pressure to give a quantitative yield
of 1 as a purple-violet powder. 1H NMR (300 MHz, CD3CN): δ =
9.16 (s, 1 H, H-5), 8.71 (t, 1 H, H-4ЈЈЈ), 8.59 (d, 2 H, H-2ЈЈЈ,6ЈЈЈ),
8.01 (t, 2 H, H-4Ј,4ЈЈ), 7.55 (m, 4 H, H-3Ј,3ЈЈ,5Ј,5ЈЈ), 7.26 (t, 2 H,
H-3ЈЈЈ,5ЈЈЈ), 2.68 (s, CH3) ppm. ESI-MS: m/z = 739 [CuL2]+, 401
[Cu4L4]4+, 339 [L]+. Cu4(L)4(PF6)4 (2187.7): calcd. C 48.31, H 3.32,
Conclusions
The novel ligand L containing two bidentate N,N-bind-
ing subunits has been prepared and its solid state conforma-
tional properties characterized by X-ray crystallography.
The reaction of L with CuI, AgI, and ZnII results in the
clean and quantitative formation of [2×2] grid-type com- N 10.24; found C 49.01, H 3.33, N 9.98.
Eur. J. Inorg. Chem. 2005, 4168–4173
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V. Patroniak, A. R. Stefankiewicz, J.-M. Lehn, M. Kubicki
FULL PAPER
Ag Complex 2: A solution of ligand L (10.0 mg, 30 µmol) and
Ag(CF3SO3) (7.6 mg, 30 µmol) in MeCN (5 mL) was stirred at
room temperature for 24 h. The white complex 2 was isolated in
quantitative yield by evaporation of the solvent. 1H NMR
(300 MHz, CDCl3): δ = 9.21 (s, 1 H, H-5), 8.73 (t, 1 H, H-4ЈЈЈ),
8.55 (d, 2 H, H-2ЈЈЈ,6ЈЈЈ), 7.91 (t, 2 H, H-4Ј,4ЈЈ), 7.58 (m, 4 H, H-
3Ј,3ЈЈ,5Ј,5ЈЈ), 7.45 (t, 2 H, H-3ЈЈЈ,5ЈЈЈ), 2.69 (s, CH3) ppm. ESI-MS:
m/z = 785 [AgL2]+, 447 [Ag4L4]4+, 339 [L]+. Ag4(L)4(CF3SO3)4·
2L·C6H14O (3160.4): calcd. C 53.97, H 3.89, N 10.64, S 4.06; found
C 54.39, H 3.83, N 10.65, S 4.10.
CH3 groups) times Ueq of the appropriate carrier atom. Relevant
crystal data are listed in Table 3, together with refinement details.
CCDC-264396 (for 1), -264397 (for 2-RT), and -264398 (for 2-LT)
contain the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments
Zn Complex 3: An equimolar mixture of Zn(CF3SO3)2 (13.3 mg,
39 µmol) and ligand L (14.2 mg, 39 µmol) in MeCN (5 mL) was
stirred at room temperature for 24 h. The solvent was evaporated
under reduced pressure to yield a pale-green complex 3 in quantita-
tive yield. ESI-MS: m/z = 889 {[Zn(L)2](CF3SO3)}+, 553 {[Zn4-
This work was partly supported by the Polish Ministry of Scientific
Research and Information Technology (grant No. 4 T09A 049 24).
[1] J.-M. Lehn, A. Rigault, J. Siegel, J. Harrowfield, B. Chevrier,
D. Moras, Proc. Natl. Acad. Sci. USA 1987, 84, 2565–2569.
[2] M. Barboiu, G. Vaughan, N. Kyritsakas, J.-M. Lehn, Chem.
Eur. J. 2003, 9, 763–769.
[3] J. E. Aguado, M. J. Calhorda, P. J. Costa, O. Crespo, V. Félix,
M. C. Gimeno, P. G. Jones, A. Laguna, Eur. J. Inorg. Chem.
2004, 3038–3047.
[4] C. Piguet, G. Bernardinelli, G. Hopfgartner, Chem. Rev. 1997,
97, 2005–2062; M. Albrecht, Chem. Rev. 2001, 101, 3457–3497.
[5] R. Krämer, J.-M. Lehn, A. DeCian, J. Fischer, Angew. Chem.
Int. Ed. Engl. 1993, 32, 703–706.
[6] P. N. W. Baxter, J.-M. Lehn, G. Baum, D. Fenske, Chem. Eur.
J. 2000, 6, 4510–4517.
[7] P. N. W. Baxter, H. Sleiman, J.-M. Lehn, K. Rissanen, Angew.
Chem. Int. Ed. Engl. 1997, 36, 1294–1296.
[8] H. Sleiman, P. N. W. Baxter, J.-M. Lehn, K. Airola, K. Ris-
sanen, Inorg. Chem. 1997, 36, 4734–4742.
[9] M. C. Jimenez-Molero, Ch. Dietrich-Buchecker, J.-P. Sauvage,
Chem. Eur. J. 2002, 8, 1455–1466.
(L)4](CF3SO3)4}4+
, ,
371 [Zn(L)2]2+ 339 [L]+, 254 {[Zn4(L)4]-
1
(CF3SO3)}7+. H NMR (300 MHz, CD3CN): δ = 9.32 (s, 1 H, H-
5), 8.64 (t, 1 H, H-4ЈЈЈ), 8.52 (d, 2 H, H-2ЈЈЈ,6ЈЈЈ), 7.99 (t, 2 H, H-
4Ј,4ЈЈ), 7.83 (m, 4 H, H-3Ј,3ЈЈ,5Ј,5ЈЈ), 7.60 (t, 2 H, H-3ЈЈЈ,5ЈЈЈ), 2.75
(s, CH3) ppm. Zn4(L)4(CF3SO3)8 (2807.7): calcd. C 41.07, H 2.58,
N 7.98, S 9.14; found C 41.12, H 2.49, N 7.77, S 9.28.
Crystal Structure Determination of Ligand and Complex 2: Diffrac-
tion data for L were collected at 291(1) K and for 2 at both 291(1)
and 100(1) K by the ω-scan technique up to 2θ = 60°, on a KUMA-
KM4CCD diffractometer[48] with graphite-monochromated Mo-Kα
radiation (λ = 0.71073 Å). The temperature was controlled by an
Oxford Instruments Cryosystems cooling device. The data were
corrected for Lorentz-polarization effects,[49] as well as for absorp-
tion, with SORTAV.[50] Unit-cell parameters were determined by
the least-squares fit of 2258 (L), 4514 (2-RT), and 3783 (2-LT) re-
flections of highest intensity, chosen from the whole experiment.
The structures were solved with SHELXS97[51] and refined with
the full-matrix least-squares procedure on F2 by SHELXL97.[52]
Scattering factors incorporated in SHELXL97 were used. All non-
hydrogen atoms were refined anisotropically; hydrogen atoms were
placed geometrically in idealized positions and refined as rigid
groups, with Uiso of the hydrogen atoms set as 1.2 (1.3 for CH2 and
[10] L. J. Ashfield, A. R. Cowley, J. R. Dilworth, P. S. Donelly, In-
org. Chem. 2004, 43, 4121–4123.
[11] A. L. Pickering, D.-L. Long, L. Cronin, Inorg. Chem. 2004, 43,
4953–4961.
[12] F. Bramsen, A. D. Bond, C. J. McKenzie, R. G. Hazell, B.
Moubaraki, K. S. Murray, Chem. Eur. J. 2005, 11, 825–831.
[13] R. L. Paul, S. M. Couchman, J. C. Jeffery, J. A. McCleverty,
Z. R. Reeves, M. D. Ward, J. Chem. Soc., Dalton Trans. 2000,
845–851.
[14] A. M. Garcia, D. M. Bassani, J.-M. Lehn, G. Baum, D. Fenske,
Chem. Eur. J. 1999, 5, 1234–1238.
[15] M. Yoshizawa, T. Kusukawa, M. Fujita, S. Sakamoto, K. Yam-
aguchi, J. Am. Chem. Soc. 2001, 123, 10454–10459.
[16] M. Yoshizawa, Y. Takeyama, T. Kusukawa, M. Fujita, Angew.
Chem. Int. Ed. 2002, 41, 1347–1349.
[17] M.-T. Youinou, N. Rahmouni, J. Fischer, J. A. Osborn, Angew.
Chem. Int. Ed. Engl. 1992, 31, 733–735.
[18] P. N. W. Baxter, J.-M. Lehn, K. Rissanen, Chem. Commun.
1997, 1323–1324.
[19] J. Rojo, M. Ruben, E. Breuning, J.-P. Giesselbrecht, J.-M.
Lehn, Angew. Chem. Int. Ed. 2000, 39, 4139–4142.
[20] E. Breuning, M. Ruben, J.-M. Lehn, F. Renz, Y. Garcia, V.
Ksenofontov, P. Gütlich, E. Wegelius, K. Rissanen, Angew.
Chem. Int. Ed. 2000, 39, 2504–2505.
[21] H. Oshio, H. Onodera, O. Tamada, H. Mizutani, T. Hikichi,
T. Ito, Chem. Eur. J. 2000, 6, 2523–2530.
[22] P. N. W. Baxter, R. G. Khoury, J.-M. Lehn, G. Baum, D. Fen-
ske, Chem. Eur. J. 2000, 6, 4140–4148.
[23] A. Marquis, J.-P. Kintzinger, R. Graff, P. N. W. Baxter, J.-M.
Lehn, Angew. Chem. Int. Ed. 2002, 41, 2760–2764.
[24] J. P. Plante, P. D. Jones, D. R. Powell, T. E. Glass, Chem. Com-
mun. 2003, 336–337.
Table 3. Crystal data, data collection, and structure refinement.
Compound
L
2
Formula
Formula mass
Crystal system
Space group
a [Å]
C22H18N4
338.40
orthorhombic
P212121
4.2565(8)
16.8939(16)
24.1686(17)
1737.9(4)
4
C142H122Ag4F12N24O13S4
3160.35
orthorhombic
Ccca
17.4365(9)
30.4319(18)
24.5520(13)
13027.9(12)
2
b [Å]
c [Å]
V [Å3]
Z
Dcalcd. [g cm–3
F(000)
]
1.293
712
0.079
1.585
6288
0.7471
µ [mm–1
]
Crystal size [mm]
Θ range [°]
hkl range
0.5×0.08×0.07
2.94–29.44
–5 Յ h Յ 2
–23 Յ k Յ 23
–33 Յ l Յ 33
11688
2576 (0.074)
0.058
0.096
0.15×0.08×0.08
2.82–29.57
–23 Յ h Յ 21
–40 Յ k Յ 40
–33 Յ l Յ 20
27152
8263 (0.094)
0.065
0.095
Reflections collected
Reflections unique (Rint
Final R(F) [I Ͼ 2σ(I)]
Final wR(F2) [all data]
Goodness of fit
)
[25] M. Ruben, E. Breuning, M. Barboiu, J.-P. Gisselbrecht, J.-M.
Lehn, Chem. Eur. J. 2003, 9, 291–299.
[26] J. Hausmann, G. B. Jameson, S. Brooker, Chem. Commun.
2003, 2992–2993.
1.060
0.14/–0.14
0.967
0.87/–0.51
Max/min ∆ρ [eÅ–3
]
4172
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 4168–4173

Grid-Type Copper(), Silver(), and Zinc() Complexes
FULL PAPER
[27] V. Patroniak, P. N. W. Baxter, J.-M. Lehn, M. Kubicki, M. Nis-
sinen, K. Rissanen, Eur. J. Inorg. Chem. 2003, 4001–4009.
[28] L. H. Uppadine, J.-P. Gisselbrecht, J.-M. Lehn, Chem. Com-
mun. 2004, 718–719.
[29] P. N. W. Baxter, J.-M. Lehn, J. Fisher, M.-T. Youinou, Angew.
Chem. Int. Ed. Engl. 1994, 33, 2284–2287.
[30] P. N. W. Baxter, J.-M. Lehn, B. O. Kneisel, D. Fenske, Chem.
Commun. 1997, 2231–2232.
[31] P. N. W. Baxter, J.-M. Lehn, B. O. Kneisel, D. Fenske, Angew.
Chem. Int. Ed. Engl. 1997, 36, 1978–1981.
[39] I. Weissbuch, P. N. W. Baxter, I. Kuzmenko, H. Cohen, S. Co-
hen, K. Kjaer, P. B. Howes, J. Als-Nielsen, J.-M. Lehn, L. Lei-
serowitz, M. Lahav, Chem. Eur. J. 2000, 6, 725–734.
[40] M. Ruben, J. Rojo, F. J. Romero-Salguero, L. H. Uppadine, J.-
M. Lehn, Angew. Chem. Int. Ed. 2004, 43, 3644–3662.
[41] B. Wiley, Y. Sun, B. Mayers, Y. Xia, Chem. Eur. J. 2005, 11,
454–463.
[42] P. Jiang, Z. Guo, Coord. Chem. Rev. 2004, 248, 205–229.
[43] N. C. Lim, H. C. Freake, C. Brückner, Chem. Eur. J. 2005, 11,
38–49.
[32] S. Toyota, C. R. Woods, M. Benaglia, R. Haldimann, K.
Wärnmark, K. Hardcastle, J. S. Siegel, Angew. Chem. Int. Ed.
2001, 40, 751–754.
[33] A. Marquis, J.-P. Kintzinger, R. Graff, P. N. W. Baxter, J.-M.
Lehn, Angew. Chem. Int. Ed. 2002, 41, 2760–2764.
[34] R. Ziessel, L. Charbonnière, M. Cesario, T. Prangé, H. Nieren-
garten, Angew. Chem. Int. Ed. 2002, 41, 975–979.
[35] R. Hoogenboom, G. Kickelbick, U. S. Schubert, Eur. J. Org.
Chem. 2003, 4887–4896.
[36] Y. Lan, D. K. Kennepohl, B. Moubaraki, K. S. Murray, J. D.
Cashion, G. B. Jameson, S. Brooker, Chem. Eur. J. 2003, 9,
3772–3784.
[37] J. R. Nitschke, M. Hutin, G. Bernardinelli, Angew. Chem. Int.
Ed. 2004, 43, 6724–6727.
[44] P. Jutzi, U. J. Gilge, J. Organomet. Chem. 1983, 246, 163–168.
[45] G. V. Long, S. E. Boyd, M. M. Harding, I. E. Buys, T. W. Ham-
bley, J. Chem. Soc., Dalton Trans. 1993, 3175–3180.
[46] K. Burdeska, H. Fuhrer, G. Kabas, A. E. Siegriest, Helv. Chim.
Acta 1981, 64, 113–152.
[47] J. K. Stille, Angew. Chem. Int. Ed. Engl. 1986, 25, 508–524.
[48] Oxford Diffraction (2003). CrysAlisCCD, User Guide v.171.
Oxford Diffraction Poland Sp., Wrocław, Poland.
[49] Oxford Diffraction (2003). CrysAlisRed, CCD data reduction
GUI v.171. Oxford Diffraction Poland Sp., Wrocław, Poland.
[50] R. H. Blessing, J. Appl. Crystallogr. 1989, 22, 396.
[51] G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467–476.
[52] G. M. Sheldrick, SHELX97 – Programs for Crystal Structure
Analysis (Release 97-2). Institut für Anorganische Chemie der
Universität, Tammanstrasse 4, 3400 Göttingen, Germany,
1998.
[38] I. Weissbuch, P. N. W. Baxter, S. Cohen, H. Cohen, K. Kjaer,
P. B. Howes, J. Als-Nielsen, G. S. Hanan, U. S. Schubert, J.-M.
Lehn, L. Leiserowitz, M. Lahav, J. Am. Chem. Soc. 1998, 120,
4850–4860.
Received: April 15, 2005
Published Online: September 8, 2005
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www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4173