Cap for copper(I) ions! metallosupramolecular solid and solution state structures on the basis of the dynamic tetrahedral [Cu(phenAr 2)(py)2]+ motif

Article abstract of DOI:10.1021/ic900657w

The tetrahedral [Cu(phenAr₂)(py)₂]⁺ coordination motif (phen = 1,10-phenanthroline; py = pyridine) conceived on the basis of the HETPYP concept (heteroleptic pyridyl and phenanthroline metal complexes) is a versatile dynam

Full text of DOI:10.1021/ic900657w

8192 Inorg. Chem. 2009, 48, 8192–8200
DOI: 10.1021/ic900657w
Cap for Copper(I) Ions! Metallosupramolecular Solid and Solution State Structures
on the Basis of the Dynamic Tetrahedral [Cu(phenAr2)(py)2]þ Motif
Michael Schmittel,*,† Bice He,† Jian Fan,† Jan W. Bats,‡ Marianne Engeser,§ Marc Schlosser, and
::
Hans-Jorg Deiseroth
::
†Center of Micro and Nanochemistry and Engineering, Organische Chemie I, Universitat Siegen,
::
Adolf-Reichwein-Strasse 2, D-57068 Siegen, Germany, ‡Institute fur Organische Chemie und Chemische
::
Biologie, Johann Wolfgang Goethe-Universitat, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main,
::
::
§
ꢀ
Germany, Kekule-Institut fur Organische Chemie und Biochemie der Universitat Bonn, Gerhard-Domagk-
::
Strasse 1, 53121 Bonn, Germany, and Anorganische Chemie I, Universitat Siegen, Adolf-Reichwein-Strasse 2,
D-57068 Siegen, Germany
Received March 24, 2009
The tetrahedral [Cu(phenAr2)(py)2]þ coordination motif (phen = 1,10-phenanthroline; py = pyridine) conceived on the
basis of the HETPYP concept (heteroleptic pyridyl and phenanthroline metal complexes) is a versatile dynamic unit for
constructing various heteroleptic metallosupramolecular pseudo-1D, 2D, and 3D structures, both in solution and the
solid state. The 2,9-diaryl substituted phenanthroline (phenAr2) serves as a capping ligand for copper(I) ions, as its
bulky nature prevents formation of the homoleptic complex [Cu(phenAr2)2]þ. Combination of the dynamic and
concave metal ligand building block [Cu(phenAr2)]þ with various pyridine (py) ligands, such as bi-, tri-, and tetra-
pyridines, opened the way to infinite 1D helicates, 2D networks, and discrete 3D hexanuclear cages, whereas spatial
integration of both phenAr2 and py units into a single ligand resulted in the formation of a Borromean-ring-type
hexanuclear cage.
Introduction
formation, in particular if one starts out from oligophenan-
throlines serving as an end-cap at several metal centers.
Herein, we would like to demonstrate that despite the weak
and dynamic binding of three ligands at a copper center, the
heteroleptic [Cu(phenAr2)(py)2]þ scenario is maintained in
all solution and solid state structures.
Because of its strong binding to various metal ions, the
parent 1,10-phenanthroline (phen) ligand has become a
versatile building block for a large number of supramolecular
self-assembled structures.3 Our group has contributed to
this field by developing labile heteroleptic combinations
using the concave [M(phenAr2)]nþ fragment as a starting
point.4 Because of the steric shielding of the metal fragment
by appropriately sized aryl groups Ar (for example,
The huge success of Fujita’s and Stang’s coordination
concepts using end-capped square-planar palladium and
platinum units has been documented over the last 15 years
in countless reports.1,2 A variety of ligands, such as pyridines,
alkynes, and nitriles, was shown to dynamically bind to the
end-capped Pd and Pt units (Scheme 1), allowing to set up
various spectacular metallosupramolecular structures, such
as squares, cages, and so forth.1 A possible limitation of the
above concepts, though, is that the kinetically inert end-cap is
not involved in the dynamic interplay. Herein, we would like
to introduce an extension of the above concepts, in which the
metal center, now a copper(I) ion, is setting up a tetrahedral
coordination scenario with one phenanthroline and two
pyridines serving as ligands (Scheme 1). Most distinctly, the
phenanthroline end-cap is not bound in a kinetically inert
fashion to the copper center, which should allow reduction of
the activation barriers in intricate multitopic aggregate
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*To whom correspondence should be addressed. E-mail: schmittel@
chemie.uni-siegen.de.
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J. R.; Gavina, P.; Martí-Gastaldo, C.; Romero, F. M.; Tatay, S. Inorg. Chem. 2008,
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5645–5647. (b) Fujita, M.; Tominaga, M.; Hori, A.; Therrien, B. Acc. Chem. Res.
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r
pubs.acs.org/IC
Published on Web 08/04/2009
2009 American Chemical Society

Article
Inorganic Chemistry, Vol. 48, No. 17, 2009 8193
Scheme 1. Caps Used for Metal Ion Complexes
Scheme 2. Dynamic Heteroleptic Complex Motifs
in combination with a flexible binding geometry, they have an
enormous potential for exciting nanostructures,1b,2b,9 in
particular in combination with poly(pyridine) building blocks
(4,40-bipyridine10 and 1,3,5-tripyridyltriazine1d).
Ar = 2,4,6-trimethylphenyl) in phenAr2, the [M(phenAr2)]nþ
unit is arrested against formation of a bishomoleptic complex
[M(phenAr2)2]nþ even if the phenAr2 is present in large excess
over the metal ion. Such a particular setting allows the
combination of the [M(phenAr2)]nþ fragment with a second,
but sterically undemanding phenanthroline to afford [M-
(phenAr2)(phen)]nþ (Mnþ = Cuþ, Agþ, Zn2þ)5 or with a
sterically unpretentious terpyridine (terpy) to yield [M(phen-
Ar2)(terpy)]nþ combinations (Mnþ = Cuþ, Hg2þ, Zn2þ).6
Two main effects aid heteroleptic aggregation in the above-
mentioned complexes: (i) maximum site occupancy7 and (ii) a
strong donor-acceptor interaction between the aryl groups
Ar of phenAr2 and the second metal bound ligand (a
phenanthroline in the HETPHEN concept, and a terpyridine
in the HETTAP approach).
The quantitative formation of heteroleptic mononuclear
complexes along the HETPHEN (HETeroleptic BisPHE-
Nanthroline Complexes)4,5 or HETTAP (HETeroleptic Ter-
pyridine And Phenanthroline Complexes)6 concept found
ample use in the quantitative preparation of polynuclear
supramolecular frameworks, such as nanosized ladders,
grids, racks, dumbbells, and other topologies.4-6 The com-
bination of several bi- or tridentate ligands at dynamically
binding metal ion centers in supramolecular assemblies,
however, operates at the cost of a slow kinetics. The latter
issue becomes more and more virulent the larger and more
intricate the supramolecular framework.6b,6c,8 It thus seemed
necessary to find the right balance between thermodynamics
and kinetics to realize a facilitated access to kinetically
demanding nanostructures. Unlike phen or terpy, non-chelat-
ing monodentate pyridine ligands provide much weaker
binding with metal ions, but because of their increased kinetics
Until now, metal complexes [M(py)2Lm]nþ with pyridine
(py) as ligand have been investigated extensively for square-
planar coordinated metal ions, such as palladium and plati-
num,1,2,11 whereas metal ions with a tetrahedral coordination
environment, as copper(I) ions, have been reported amaz-
ingly seldom.12 Therefore, as an extension of the HETPHEN
concept,4 we seeked to explore the HETPYP approach
(HETeroleptic PYridyl and Phenanthroline metal complex-
es), which brings together pyridine and phenanthroline
ligands at a tetrahedrally coordinating metal center to form
dynamic [M(phenAr2)(py)2]nþ complexes (Scheme 2, right).
While this method should work equally well for Cuþ, Agþ,
and Zn2þ, we have concentrated our first efforts on copper(I)
ions. As a prerequisite, we used a phenanthroline that is
shielded by large 2,9-aryl groups (phenAr2) in a way that its
complexation process in absence of pyridine ligands will
arrest at the [Cu(phenAr2)]þ exposing two vacant coordina-
tion sites (usually occupied by loosely bound solvent
molecules). In a way, the [Cu(phenAr2)]þ unit is a capped
metal center analogous to M(Me2N-X-NMe2) or M(Ph2P-X-
PPh2) with M = Pd, Pt. We will demonstrate that such an
approach opens structural options for simple and intricate
complexes that are complementary to the well-known palla-
dium and platinum chemistry.
All ligands used in this report are depicted in Scheme 3.
4,40-Bipyridine (BP) and the tetrakispyridine TPP were
purchased and used as supplied without further puri-
fication. Phenanthrolines Phen16a and Phen26a as well as
tripyridine TP13 were prepared according to literature pro-
cedures. Phen3 was prepared as described in the Supporting
Information.
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8194 Inorganic Chemistry, Vol. 48, No. 17, 2009
Scheme 3. Ligands Used in the Present Study
Schmittel et al.
Results and Discussion
solution was obtained immediately. A 1H NMR spectrum
of this solution exhibited no shifts for the protons differ-
ent from those of the free constituents, suggesting that
acetonitrile had eventually broken up the [(phenAr2)-
Cu(I)]---py coordination releasing free BP. An ESI FT-
ICR MS spectrum of this solution surprisingly revealed
not only signals of small fragments, such as [Cu(Phen2)-
(BP)]þ and [Cu2(Phen2)2(BP)(PF6)]þ, but also of larger
aggregates, like [Cu3(Phen2)3(BP)2(PF6)2]þ. Combining
the evidence from 1H NMR and the ESI FT-ICR MS, it
seems plausible that the addition of acetonitrile reduced
the [(phenAr2)Cu(I)]---py coordination in solution by
increasing the dynamic exchange at the metal center.
However, under the vacuum conditions of the mass
spectrometry experiment, that is, after removal of aceto-
nitrile, a substantial fraction of [(phenAr2)Cu(I)]---py
coordinated fragments showed up as demonstrated by
the ESI FT-ICR MS results.
Pseudo-1D Supramolecular Helicates. Our first idea
aimed at using the heteroleptic complex motif
[Cu(phenAr2)(py)2]þ to construct a supramolecular poly-
gon, which we expected to form from Phen1 and BP (1:1)
in the presence of 1 equiv of [Cu(MeCN)4]PF6 despite
some angular strain at the tetrahedrally coordinated
metal center in dichloromethane. When we dissolved
the corresponding product in dichloromethane-d2, the
1H NMR spectrum showed the expected set of sharp
signals indicative of the formation of a single species.
Notably, the chemical shifts of both protons of BP were
dramatically upfield shifted from 8.71 to 7.75 and from
7.55 ppm to 7.39 ppm because of the BP protons being
positioned in the shielding region of mesityl groups of
Phen1. Because of the identical shielding of both pyridine
rings in BP, one is led to postulate the formation of
polygons or an infinite linear arrangement. ESI FT-ICR
MS spectra of the solution, however, showed only signals
representing small fragments such as [Cu(Phen1)(BP)]þ
and [Cu2(Phen1)2(BP)(PF6)]þ, clearly witnessing a weak
Fortunately, single crystals suitable for X-ray analysis
were obtained by slow evaporation of acetonitrile from a
1,2-dichlorobenzene/acetonitrile solution of Phen2, BP,
and [Cu(MeCN)4]PF6 (1:1:1). The resultant product is
denoted as complex 2 in the following. As depicted in
Figure 1, each copper(I) ion, as expected, is tetrahedrally
coordinated by two nitrogen atoms from one phenan-
throline and two nitrogen atoms from two bipyridines.
Each bipyridine BP connects two copper-phenanthroline
units, which leads to the formation of a one-dimensional
(1D) structure. Furthermore, the crystal structure of
complex 2 displays right-handed and left-handed heli-
coordination bond in [Cu(phenAr2)]þ py aggregates,
3 3 3
which as a consequence do not fully survive gas phase
ionization. Unfortunately, although single crystals of
rather big size and good shape were obtained by different
methods and in different solvents, all crystals proved to be
unstable during diffraction measurements. Even at low
temperature, the crystal broke up easily, and even wrap-
ping up in oil or locating in the original solvent would not
prolong its stability.
Importantly, changing the ligand Phen1 to Phen2
caused a big difference. When Phen2 and BP (1:1) were
combined with 1 equiv of [Cu(MeCN)4]PF6 in dichloro-
methane-d2, small crystals precipitated out in less than 10
cates with a pitch of 27.6 A, rather than zigzag chains12a as
˚
reported by Blake et al., who used a simple unsubstituted
phenanthroline in combination with BP. Each helicate
propagates along the c axis, generating a prismatic cavity
2
1
˚
with an opening of about 8.7 ꢀ 8.7 A . In complex 2, any
min, precluding the measurement of the H NMR spec-
trum. This finding already suggested that bigger aggre-
gates, possibly oligomers or polymers, were formed in
solution. Upon addition of 5% (v/v) of acetonitrile-d3 to
the precipitated complex (in dichloromethane), a clear
left-handed helicate is surrounded by four right-handed
helicates with interpenetration of their grooves, and vice
versa (Figure 1, left). The PF6 anions are located
-
in between two Cu(I) coordination centers from two

Article
Inorganic Chemistry, Vol. 48, No. 17, 2009 8195
Figure 1. (Top left) Top view of the crystal packing of complex 2 with left- and right-handed helicates in red and blue, respectively. The capping ligand
Phen2, solvate molecules, anions, and hydrogen atoms were omitted for clarity. (Top right) Top view of crystal packing of complex 2 with hydrogen atoms
omitted for clarity. Carbon, gray; Nitrogen, blue; Copper, red (hidden); Phosphorus, Orange; Fluorine, yellow; Chlorine, green. (Bottom) Side view of the
X-ray structure showing a right-handed helix of complex 2. Carbon, gray; Nitrogen, blue; Copper, green. Solvate molecules, anions and hydrogen were
omitted for clarity.
adjacent helicates. Related PF6- anions and Cu(I) cations
are exactly located on a straight line (Figure 1, right). All
1,2-dichlorobenzene solvate molecules are located inside
channels a formed by a single helicate, while channels b
formed by four adjacent helicates remain empty.
From the data it seems that both in solution and in the
solid state the combination of Phen2, BP, and
[Cu(MeCN)4]PF6 (1:1:1) leads to coordination polymers
[Cu(Phen2)(BP)]nnþ. The high lability and weak Cu--py
coordination does not allow to differentiate between
linear or cyclic oligomers in solution, for which there
are some precedents with copper in oxidation state 2þ.14
From the above results it becomes clear that the
[Cu(phenAr2)(py)2]þ is a continual motif with Phen1/
Phen2 and BP recurring both in the solid state and
solution, with the restriction that 1H NMR and ESI
FT-ICR MS do not allow a full structural identification
Figure 2. HyperChem structure of cage 3c. Carbon, cyan; Nitrogen,
blue; Copper, green; Hydrogen, white. The ligandPhen1 bound to each of
the six copper centers was omitted for clarity.
in the latter medium.
From a Truncated Tetrahedron to a Broken Honeycomb
Network. Encouraged by the successful application of
the [M(phenAr2)(py)2]nþ motif as illustrated by the for-
mation of complex 2, we seeked to replace bipyridine
BP by tripyridine TP. With py in [M(phenAr2)(py)2]nþ
being represented by TP we envisioned that the
smallest supramolecular entity formed at lowest entropic
costs and correct maximum site occupancy should be the
hexanuclear [Cu6(Phen1)6(TP)4]6þ cage. Indeed, combi-
nation of Phen1, TP and [Cu(MeCN)4]PF6 (6:4:6) in
dichloromethane resulted in the formation of the Fujita
type of truncated tetrahedral cage9a,15 3c (c for cage,
Figure 2) as demonstrated by solution characterization
techniques, while crystallization led to another structure,
the broken honeycomb network, herein denoted as 3n (see
Figure 4, n for network).
Undoubtedly, the solution structure 3c is different from
the solid state structure 3n on the basis of all data. For
example, the H NMR of 3c, exhibiting a single set of
1
(14) Liu, G.-F.; Ren, Z.-G.; Li, H.-X.; Chen, Y.; Li, Q.-H.; Zhang, Y.;
Lang, J.-P. Eur. J. Inorg. Chem. 2007, 5511–5522. Al-Rasbi, N. K.; Adams, H.;
Harding, L. P.; Ward, M. D. Eur. J. Inorg. Chem. 2007, 4770–4780.
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R. Angew. Chem., Int. Ed. Engl. 1996, 35, 1690–1692.

8196 Inorganic Chemistry, Vol. 48, No. 17, 2009
Schmittel et al.
signals, is characterized by large upfield shifts of the
pyridine protons of TP to 7.65 and 7.28 ppm! Equally,
the DOSY NMR spectrum confirmed the formation of a
single product (see Supporting Information). Though the
binding in complex 3c was not strong enough to survive
standard ESI-MS conditions, the ESI FT-ICR MS ana-
lysis provided clear clues for the existence of the hexa-
nuclear cage 3c in solution by showing the corresponding
signals: m/z 2577.2 Da for [Cu6(Phen1)6(TP)4)(PF6)4]2þ
)
and fragments thereof (2264.8 Da, [Cu5(Phen1)5(TP)4)-
(PF6)3]2þ; 2053.2 Da, [Cu5(Phen1)5(TP)3)(PF6)3]2þ; 1951.7
; 1740.1 Da, [Cu4-
Da, [Cu4(Phen1)4(TP)4)(PF6)2]2þ
(Phen1)4(TP)3)(PF6)2]2þ; and so on).
After slow vapor diffusion of diethylether into the
solution of complex 3c in dichloromethane, red needle-
shaped crystals were obtained, but they were too small to
be measured. After dissolving the complex in a mixture of
acetonitrile and dichlorobenzene (10:1) in a small vial and
after allowing slow evaporation of acetonitrile to occur,
big crystals in form of red rods were obtained that proved
to be insoluble in dichloromethane. As already mentioned
above, the solid state structure of complex 3n (Figure 3)
showed a two-dimensional (2D) honeycomb arrange-
ment rather then a truncated tetrahedron as postulated
for 3c.
Figure 3. Top view of crystal structure of complex 3n. Solvate molecules
were omitted for clarity.
Cu-TPP, all our attempts failed. Since the low solubility
of metal porphyrins is a consequence of self-aggregation
via metal--pyridine association,17 it was envisioned to
start out from the free base porphyrin TPP with its
increased solubility instead. If self-assembly along the
HETPYP concept were faster than metal insertion into
TPP to yield Cu-TPP, a kinetically controlled solid state
assembly could potentially form. As the transformation
of TPP to Cu-TPP in a reaction system containing
[Cu(MeCN)4]PF6 cannot be prevented with time, we have
to make sure that 100% of TPP will be converted to Cu-
TPP by adding some extra amount of [Cu(MeCN)4]PF6.
On the basis of these considerations, a mixture of Phen1,
TPP, and [Cu(MeCN)4]PF6 (2:1:3) in dichlorobenzene/
acetonitrile (8:2) was heated to reflux for 2 h. After
cooling to room temperature and slow evaporation
of acetonitrile, single crystals of complex 4 suitable for
X-ray diffraction measurement were obtained.
The X-ray analysis, unfortunately of low quality, re-
vealed a 2D broken honeycomb network with huge pores,
2
each of which exhibited a size of about 780 A . Every
˚
single pore contains six TP ligands and six Cu-Phen
species (Figure 3), and actually represents a combination
of three adjacent hexagons of a classical honeycomb
(Figure 4, left). The 2D sheets do not overlap with each
other in a perfect superimposition, which would result in a
2
˚
pore size of the channels of 780 A . Rather, the 2D sheets
are shifted relative to each other by about 1.0 nm (from
ideal superimposition), thereby forming hexagonal chan-
2
nels with a smaller opening of about 260 A (Figure 4,
˚
right). All solvate molecules and anions are located in
those channels. Since in the solution state, the combina-
tion of Phen1, TP, and [Cu(MeCN)4]PF6 (6:4:6) resulted
1
in a discrete cage as postulated on the basis of the H
NMR, DOSY, and FT-ICR MS, the different solid
state structure is presumably due to solid state effects
resulting from crystal packing, solvate effects and so on.16
Notably, once again the [Cu(phenAr2)(py)2]þ unit proved
to be a continual motif in both solution and the solid
state, now with TP as a pyridine ligand.
Porphyrinic Network. To further challenge the exclu-
sive formation of the [Cu(phenAr2)(py)2]þ unit with a
tetrapyridine ligand, the reaction of the capping phenan-
throline Phen1 and copper(I) ions with the tetrapyridine
TPP was probed. This combination is even more inter-
esting, as the reaction of copper(II)-filled TPP with
[Cu(MeCN)4]X has been reported to lead to three-dimen-
sional (3D) networks with large channels.17 To probe the
self-assembly along the HETPYP approach, the reaction
of Phen1, Zn-TPP (or Cu-TPP), and [Cu(MeCN)4]PF6
(2:1:2) in various solvents system was explored. However,
because of the extremely low solubility of Zn- and
Though the crystal quality of 4 was not very high, a
structure determination was still possible. From the
X-ray structure shown in Figure 5, it becomes apparent
that each porphyrin unit is now filled with a copper ion.
While in complex 2, the Cu-Phen motifs are connected by
a bifurcate ligand (BP) to form the 1D helicate, in
complex 4, the Cu-Phen motifs are linked by a tetrafur-
cate ligand (Cu-TPP) to generate a 2D structure. Each
copper(I) is tetrahedrally coordinated as observed in 4.
The planes of two adjacent porphyrin units around one
copper(I) center are perpendicular to each other
(Figure 6), resulting in a puckered layer structure. Any
of the Cu-TPP ligand connects to four Cu-TPP units and
every four Cu-TPP units form a big cavity with a size of
2
˚
about 13.4 ꢀ 24.1 A (estimated by the distance of the
diagonal copper ions within one cavity), where anions,
solvate molecules, and the bulky groups at 2,9-position
of Phen1 are accommodated. The phenanthroline ligand
Phen1 acts like a scissor cutting the Robson’s 3D net-
works into 2D sheets by replacing the two pyridyl units
delivered by two Cu-TPP ligands (as in solution) by a
(16) Pentecost, C. D.; Chichak, K. S.; Peters, A. J.; Cave, G. W. V.;
Cantrill, S. J.; Stoddart, J. F. Angew. Chem., Int. Ed. 2007, 46, 218–222.
(17) Abrahams, B. F.; Hoskins, B. F.; Michail, D. M.; Robson, R. Nature
1994, 369, 727–729.

Article
Inorganic Chemistry, Vol. 48, No. 17, 2009 8197
Figure 4. X-ray structure of complex 3n. Left: space filling presentation of a single layer of the tripyridine/Cuþ skeleton of 3n (phenanthrolines are omitted
for clarity). Right: stick presentation of the multilayer network of 3n (solvate molecules, anions, and hydrogen were omitted for clarity).
Figure 5. X-ray structure of complex 4. Carbon, gray; Nitrogen, blue; Copper, green. Ligand Phen1, solvate molecules, anions, and hydrogen atoms were
omitted for clarity.
single Phen1 ligand. The N(Py)-Cu-N(Py) angle is
104.2°.
Cage 5 was fully characterized by ordinary ESI-MS
with the spectrum showing a clear set of signals corre-
sponding to the expected cage with a charge range from
3þ to 6þ (see Supporting Information). The facile ESI-
MS characterization of cage 5 indicated that because of
the mutual binding of in total six Phen3, all parts are held
together more tightly than in 3c. The 1H NMR spectrum
of cage 5 showed a clear single set of signals with upfield
shifts for the py 7-H protons. Besides, the DOSY spec-
trum of cage 5 confirmed the formation of a single
product by showing a single set of signals (see Supporting
Information).
Hexanuclear Cage (Borromean-Ring-Type Structure).
All experiments delineated above have shown a high
fidelity in the formation of the [Cu(phenAr2)(py)2]þ
motif, in both solution and the solid state. For testing a
sterically congested self-assembly process, we decided to
spatially integrate the phenAr2 and the py coordination
motifs into a single ligand, as realized in Phen3. Reaction
of Phen3 and [Cu(MeCN)4]PF6 (1:1) afforded smoothly
the hexanuclear cage 5 (Figure 7), whose smaller analogue
had been reported earlier by Champness et al., though
without control of heteroleptic aggregation.18 Hence,
while the phenAr2 unit in Phen3 ascertains heteroleptic
aggregation at the copper(I) center, this is no conditio sine
qua non for systems with a spatial integration of the
phenanthroline and pyridine unit.
From the X-ray structure, depicted in Figure 7, cage 5
has the structure of Borromean rings.19 In each case, two
ligands Phen3 and two Cu(I) metal ions form one rhom-
bus (or ring), and the resulting three rhombuses are
(19) (a) Chichak, K. S.; Cantrill, S. J.; Pease, A. R.; Chiu, S.-H.; Cave, G.
W. V.; Atwood, J. L.; Stoddart, J. F. Science 2004, 304, 1308–1312. (b)
Cantrill, S. J.; Chichak, K. S.; Peters, A. J.; Stoddart, J. F. Acc. Chem. Res. 2005,
38, 1–9.
::
(18) Dolomanov, O. V.; Blake, A. J.; Champness, N. R.; Schroder, M.;
Wilson, C. Chem. Commun. 2003, 682–683.

8198 Inorganic Chemistry, Vol. 48, No. 17, 2009
Schmittel et al.
Figure 6. X-ray structure of complex 4. Carbon, gray; Nitrogen, blue; Copper, green. Solvate molecules, anions, and hydrogen atoms were omitted for
clarity.
ratio around 5:1, suggesting that the cavity accommo-
dates one out of the six PF6 anions as a guest. In
contrast, the cavity of the truncated tetrahedral cage 3c
-
3
is much larger with 2700 A in volume (calculated from
˚
HyperChem structure, Figure 2). Since the cavity of 3c in
addition has rather large portals, anions may go into and
out easily. Indeed, for 3c 31P and 19F NMR studies
showed only one set of signals.
Conclusion
Our concept to use 2,9-aryl substituted phenanthrolines
to dynamically cap copper(I) ions and to set up a tetra-
hedral [Cu(phenAr2)(py)2]þ metal junction allowing for
dynamic heteroleptic aggregation with pyridine ligands
proved to be successful in both solution and the solid state,
as the combination of the concave [Cu(phenAr2)]þ with
the corresponding bi-, tri-, and tetra-pyridyl compounds
resulted in a series of supramolecular structures. Because
of the highly dynamic and thermochemically weak copper-
(I)-pyridine interaction in solution, the resulting struc-
Figure 7. X-ray structure of cage 5. Solvate molecules, anions, and
hydrogen were omitted for clarity.
tures still pose a challenge to our present arsenal of
analytical tools thus requiring the improvement of solu-
tion state characterization, in particular since aggregation
in solution and the solid state in the present examples
sometimes led to different structures.
interlocked with each other via copper(I) coordination
centers, at which the phenanthroline and pyridyl units act
as endo and exo binding ligands, respectively. Since the
two arms of Phen3 comprise an angle of 60°, the angle of
Npy-Cu-Npy should be 120° according to the geometry
of a rhombus. This is in good agreement with the experi-
mental value of 116.2° indicating that each arm is only
distorted from the ideal angle by about 1.9°. The cavity of
Unlike the bidentate ligands 2,2-bipyridine or 1,10-phe-
nanthroline, monodentate pyridyl ligands at the copper(I)
center form a N(py)-Cuþ-N(py) coordination angle ran-
ging from 101.2 to 116.2°. This provides the desired increased
flexibility useful for the design of highly complicated nanos-
tructures and possibly lower barriers for dynamic repair.
Work is in progress to demonstrate the ample usefulness of
this concept.
3
˚
cage 5 is around 610 A in size calculated from the
positions of the Cu(I) coordination centers. Both 31P
and 19F NMR spectra show two sets of signals with a

Article
Inorganic Chemistry, Vol. 48, No. 17, 2009 8199
Table 1. Summary of Crystallographic Data for Complexes 2, 3n, 4, and 5
2
3n
4
5
formula
Fw
Space group
C
44H36Cl2CuF6N4P
C432H340Cl44Cu6F36N24P6
8678.14
P21/n
23.226(9)
29.228(11)
64.59(3)
97.852(18)
43438(30)
4
1.327
0.1501
0.1990
C124H96Cl8Cu3F12N12P2
2518.29
P21/c
14.248(3)
16.735(3)
25.463(5)
100.13(3)
5977(2)
2
1.399
0.1205
0.2994
C125H98Cl11Cu2F12 N8P2
2519.08
R3
26.457(11)
26.457(11)
102.846(8)
90.00
62345(37)
18
1.208
0.0709
0.1748
900.18
I41/acd
24.789(4)
24.789(4)
27.611(6)
90.00
16967(5)
16
1.410
˚
a/A
˚
b/A
˚
c/A
β/deg
3
˚
V/A
Z
Dcalc (g cm-3
)
R1 [I > 2σ(I)]
wR2 [I > 2σ(I)]
0.0528
0.0999
Experimental Part
1354, 1216, 1124, 1033, 867, 838, 779, 751, 557 cm-1; 1H NMR
(400 MHz, CD2Cl2:CD3CN (19:1)): δ = 8.67 (d, J = 8.2 Hz,
2H, 2-H), 8.21 (dd, J = 6.3 Hz, 1.6 Hz, 4H, a-H), 8.15 (s, 2H, 1-
H), 7.86 (d, J = 8.2 Hz, 2H, 3-H), 7.45 (dd, J = 6.3 Hz, 1.6 Hz,
4H, b-H), 7.25 (t, J = 7.8 Hz, 2H, 6-H), 7.08 (d, J = 7.8 Hz, 4H,
5-H), 1.92 (s, 12H, 4-H); 13C NMR (100 MHz, CD2Cl2:CD3CN
(19:1)): δ = 159.8, 150.7, 145.5, 143.9, 140.0, 138.4, 136.0, 129.3,
128.3, 127.8, 127.1, 126.8, 121.8, 20.0; FT-ICR MS: calcd for
[Cu(Phen2)(BP)]þ: m/z 607.2, found: m/z 607.2, calcd for
[Cu2(Phen2)2(BP)(PF6)]þ: m/z 1203.3, found: m/z 1203.3, calcd
for [Cu3(Phen2)3(BP)2(PF6)2]þ: m/z 1958.4, found: m/z 1957.5;
All commercial reagents were used without further purifi-
cation. The purification and drying of the solvents was
accomplished according to standard methods. Thin-layer
chromatography was performed using thin-layer chromato-
graphy plates (Merck, Silica Gel 60 F254). Silica Gel 60 was
equally used for column chromatography. Confirmation of
the structures of all products was obtained by 1H NMR and
13C NMR spectroscopy (Bruker AC 200 and Avance 400
spectrometer, using the deuterated solvent as the lock and
residual protiated solvent as the internal reference). 19F and
31P NMRs were measured without reference to see whether
Anal. Calcd for C38H32CuF6N4P C6H4Cl2 ([Cu(Phen2)-
3
-
(BP)(PF6)] 1,2-dichlorobenzene): C, 58.71; H, 4.03; N, 6.22;
3
the PF6 ions were free ions or involved in host-guest
found C, 58.38; H, 3.64; N, 6.30. Single crystals suitable for
X-ray analysis were obtained by slow evaporation of acetonitrile
from a 1,2-dichlorobenzene/acetonitrile (4:1) solution of Phen2,
BP, and [Cu(MeCN)4]PF6 (1:1:1). For the solid state character-
ization, see the X-ray structural analysis.
complexes. The numbering of carbon atoms of the molecular
formulas shown in the Experimental Section is only used for
the assignment of the NMR signals and is not in accordance
with the IUPAC nomenclature rules. Melting points were
taken using an apparatus of Dr. Tottoli (Buchi) and are
::
Complex 3c (Solution State Characterization). 2,9-Dimesityl-
phenanthroline (Phen1, 4.16 mg, 10.0 μmol) and [Cu-
(MeCN)4]PF6 (3.73 mg, 10.0 μmol) were dissolved in dichlor-
omethane (0.50 mL) affording a yellowish solution. Then, 1,3,5-
trimethyl-2,4,6-tris(4-pyridinylethynyl)benzene13 (TP, 2.82 mg,
6.66 μmol) was added whereupon the yellow color intensified.
After removal of the solvent, the solid residue was analyzed by
FT-ICR MS, 1H NMR, 13C NMR, DOSY, and elemental analysis
without any further purification. mp: >300 °C; IR (KBr): = ν~
2919, 2207, 1606, 1492, 1481, 1379, 1357, 1214, 1148, 1111, 870,
841, 558 cm-1; 1H NMR (400 MHz, CD2Cl2): δ= 8.72 (d, J = 8.3
Hz, 12H, 2-H), 8.19 (s, 12H, 1-H), 7.93 (d, J = 8.3 Hz, 12H, 3-H),
7.65 (d, J = 6.3 Hz, 24H, a-H), 7.28 (d, J = 6.3 Hz, 24H, b-H),
6.97 (s, 24H, 5-H), 2.78 (s, 36H, c-H), 2.36 (s, 36H, 6-H) 2.01 (s,
72H, 4-H); 13C NMR (100 MHz, CD2Cl2): δ = 160.8, 150.0,
144.9, 144.0, 139.8, 139.5, 137.4, 136.1, 132.5, 129.1, 128.4, 127.5,
127.2, 126.2, 121.0, 95.0, 92.5, 21.2, 20.6/20.4; FT-ICR MS: calcd
for [Cu(Phen1)(TP)]þ: m/z 902.3, found: m/z 902.4; calcd for
[Cu3(Phen1)3(TP)2(PF6)]2þ: m/z 1216.2, found: m/z 1215.9, calcd
for [Cu2(Phen1)2(TP)(PF6)]þ: m/z 1528.7, found: m/z 1528.5;
calcd for [Cu4(Phen1)4(TP)3(PF6)2]2þ: m/z 1740.4, found: m/z
1740.1; calcd for [Cu4(Phen1)4(TP)4(PF6)2]2þ: m/z 1952.2, found:
m/z 1951.7; calcd for [Cu5(Phen1)5(TP)3(PF6)3]2þ: m/z 2053.0,
found: m/z 2053.2; calcd for [Cu5(Phen1)5(TP)4(PF6)3]2þ: m/z
2264.7, found: m/z 2264.8; calcd for [Cu6(Phen1)6(TP)4-
(PF6)4]2þ: m/z 2577.2, found: m/z 2577.2; Anal. Calcd for
C300H252Cu6F36N24P6 2CH2Cl2 ([Cu6(Phen1)6(TP)4(PF6)6] 2-
uncorrected. Electrospray mass spectra (ESI-MS) were re-
corded using a ThermoQuest LCQ Deca. The purity of all
compounds was checked by thin-layer chromatography on
SiO2 (Merck, silica gel 60 F254). Infrared spectra were re-
corded on a Perkin-Elmer 1750 FT-IR spectrometer.
Complex 1 (Solution State Characterization). Ligand Phen1
(4.16 mg, 10.0 μmol) and [Cu(MeCN)4]PF6 (3.73 mg, 10.0 μmol)
were dissolved in dichloromethane (0.50 mL) affording a
slightly yellow solution. Then, 4,40-bipyridine (BP, 1.56 mg,
10.0 μmol) was added resulting in an intensification of the
yellow color. After removal of the solvents the solid residue
was analyzed by FT-ICR MS, 1H NMR, 13C NMR, and
elemental analysis without any further purification. The experi-
mental evidence strongly supports the formation of [Cu-
(Phen1)(BP)]nnþ in solution. mp: >300 °C; IR (KBr): = ν~ 3450,
2921, 1601, 1509, 1482, 1442, 1411, 1378, 1355, 1147, 1111, 840,
625, 558 cm-1; 1H NMR (400 MHz, CD2Cl2): δ = 8.72 (d, J = 8.3
Hz, 2H, 2-H), 8.19 (s, 2H, 1-H), 7.92 (d, J = 8.3 Hz, 2H, 3-H), 7.75
(d, J = 6.1 Hz, 4H, a-H), 7.39 (d, J = 6.1 Hz, 4H, b-H), 6.96 (s,
4H, 5-H), 2.32 (s, 6H, 6-H), 2.01 (s, 12H, 4-H); 13C NMR (100
MHz, CD2Cl2): δ = 160.8, 151.0, 145.6, 144.0, 139.7, 139.5, 137.4,
136.2, 129.1, 128.4, 127.5, 127.2, 122.1, 21.2, 20.4; FT-ICR MS:
calcd for [Cu(Phen1)(BP)]þ: m/z 635.2, found: m/z 635.2, calcd for
[Cu2(Phen1)2(BP)(PF6)]þ: m/z 1261.4, found: m/z 1261.4; Anal.
Calcd for C40H36CuF6N4P 0.5MeCN ([Cu(Phen1)(BP)-
3
(PF6)] 0.5MeCN): C, 61.42; H, 4.71; N, 7.86; found C, 61.09; H,
4.46; N, 7.82.
3
3
3
CH2Cl2): C, 64.61; H, 4.60; N, 5.99; found C, 64.46; H, 4.24;
N, 5.96.
Complex 2 (Solution and Solid State Characterization). Li-
gand Phen2 (3.88 mg, 10.0 μmol) and [Cu(MeCN)4]PF6 (3.73
mg, 10.0 μmol) were dissolved in a mixture of dichloromethane
and acetonitrile (0.50 mL, 19:1) to afford a slightly yellow
solution. After addition of 4,40-bipyridine (BP, 1.56 mg, 10.0
μmol), the yellow color of the solution intensified. After removal
of the solvents, the solid residue was analyzed by FT-ICR MS,
1H NMR, and 13C NMR without any further purification.
mp: >300 °C; IR (KBr): = ν~ 3070, 1602, 1584, 1498, 1412,
Complex 3n. Single crystals suitable for X-ray analysis were
obtained by slow evaporation of acetonitrile from a 1,2-dchloro-
benzene/acetonitrile solution of Phen1, TP, and [Cu-
(MeCN)4]PF6 (6:4:6). For the solid state characterization, see
the X-ray structural analysis.
Complex 4 (Solid State Characterization). 2,9-Dimesitylphe-
nanthroline (Phen1, 3.88 mg, 10.0 μmol) and [Cu(MeCN)4]PF6

8200 Inorganic Chemistry, Vol. 48, No. 17, 2009
Schmittel et al.
a
˚
Table 2. Selected Bond Distances (A) and Angles (deg) for 2, 3n, 4, and 5
1061, 1032, 999, 893, 855, 798, 757, 716, 625, 494 cm-1. For the
solid state characterization, see the X-ray structural analysis.
Because of the low solubility of Cu-TPP and Zn-TPP, free base
porphyrin of TPP was used. By copper insertion TPP was
completely converted to Cu-TPP.
2
Cu1-N1
2.043(3)
130.54(12)
108.01(11)
Cu1-N2
2.073(3)
101.17(16)
81.90(17)
N1-Cu1-N2
N1-Cu1-N1#1
N2-Cu1-N2#1
N1-Cu1-N2#1
Complex 5 (Solution State Characterization). Phen3 (5.99 mg,
10.0 μmol) and [Cu(MeCN)4]PF6 (3.73 mg, 10.0 μmol) were
dissolved in dichloromethane (0.50 mL) to afford yellow solu-
tion. After removal of solvent the solid residue was analyzed by
FT-ICR MS, 1H NMR, 13C NMR, DOSY, and elemental
analysis without any further purification. mp: >300 °C; IR
(KBr): = ν~ 2964, 1607, 1585, 1504, 1416, 1385, 1356, 1262, 1098,
3n
Cu1-N12
1.970(8)
2.068(8)
1.988(8)
2.068(8)
1.966(8)
2.075(8)
1.980(8)
2.083(8)
1.995(8)
2.063(8)
1.953(9)
2.059(8)
116.7(3)
96.6(3)
112.7(3)
108.3(3)
109.6(3)
105.6(3)
136.7(3)
94.9(3)
Cu1-N11
2.046(8)
2.120(9)
2.065(8)
2.082(8)
2.057(8)
2.153(9)
2.079(8)
2.083(8)
2.013(8)
2.063(8)
2.040(8)
2.067(8)
134.7(3)
110.8(3)
79.9(3)
Cu1-N24
Cu1-N23
Cu2-N4
Cu2-N2
Cu2-N17
Cu2-N18
Cu3-N3#2
Cu3-N14
1019, 876, 843, 804, 577, 558 cm-1 1H NMR (400 MHz,
;
Cu3-N1
Cu3-N13
acetone-d6): δ = 9.01 (d, J = 8.3 Hz, 12H, 2-H), 8.46 (s, 12H,
1-H), 8.36-8.39 (m, 12H, 7a-H), 8.18-8.20 (m, 12H, 7b-H),
8.01(dd, J = 8.3 and 2.0 Hz, 12H, 3-H), 7.29-7.31 (m, 12H, 6a-
H), 7.12-7.21 (m, 12H, 6b-H), 1.79 (s, 72H, 4-H) 1.61 (s, 72H,
5-H); 13C NMR (100 MHz, acetone-d6): δ = 161.1, 153.3,
153.1, 153.4, 149.9, 145.1, 141.9, 140.0, 139.2, 132.9, 131.4,
129.9, 128.3, 126.9, 126.6, 18.8, 18.7; ESI-MS: calcd for [M-
Cu4-N8
Cu4-N22
Cu4-N10
Cu4-N21
Cu5-N7#3
Cu5-N6
Cu5-N16
Cu5-N15
Cu6-N9
Cu6-N19
Cu6-N5
Cu6-N20
N12-Cu1-N11
N11-Cu1-N24
N11-Cu1-N23
N4-Cu2-N2
N2-Cu2-N17
N2-Cu2-N18
N3#2-Cu3-N14
N14-Cu3-N1
N14-Cu3-N13
N8-Cu4-N22
N22-Cu4-N10
N22-Cu4-N21
N7#3-Cu5-N6
N6-Cu5-N16
N6-Cu5-N15
N16-Cu5-N15
N19-Cu6-N5
N19-Cu6-N20
N12-Cu1-N24
N12-Cu1-N23
N24-Cu1-N23
N4-Cu2-N17
N4-Cu2-N18
N17-Cu2-N18
N3#2-Cu3-N1
N3#2-Cu3-N13
N1-Cu3-N13
N8-Cu4-N10
N8-Cu4-N21
N10-Cu4-N21
N7#3-Cu5-N16
N7#3-Cu5-N15
N9-Cu6-N19
N9-Cu6-N5
N9-Cu6-N20
N5-Cu6-N20
6(PF6)]6þ: m/z 662.3, found: m/z 662.6, calcd for [M-5(PF6)]5þ
:
m/z 823.8, found: m/z 823.6, calcd for [M-4(PF6)]4þ: m/z
1066.0, found: m/z 1066.8, calcd for [M-3(PF6)]3þ: m/z
126.0(3)
122.9(3)
81.1(3)
1469.6, found: m/z 1469.1; Anal. Calcd for C252H228-
Cu6F36N24P6 6CH2Cl2 2CH3CN ([Cu6(Phen3)6(PF6)6] 6CH2-
Cl2 2CH3CN): C, 57.89; H, 4.56; N, 6.70; found C, 57.55; H,
3
3
3
118.0(3)
111.8(3)
107.8(3)
108.6(3)
124.6(3)
103.9(3)
121.4(3)
118.3(3)
133.6(3)
107.6(4)
123.7(4)
102.4(3)
3
4.62; N, 6.74. Single crystals suitable for X-ray analysis were
obtained by slow vapor diffusion of diethyl ether into a 1,2-
dichlorobenzene solution of Phen3 and [Cu(MeCN)4]PF6 (1:1).
For the solid state characterization, see the X-ray structural
analysis.
80.4(3)
132.0(3)
102.7(3)
79.8(3)
109.4(3)
108.7(3)
114.8(3)
81.8(3)
X-ray Data Collection and Structure Determinations. X-ray
single-crystal diffraction data for complexes 2, 4, and 5 were
collected on a STOE IPDS one-circle image plate diffractometer
and for 3n on a SIEMENS SMART diffractometer. The struc-
tures were solved using SHELXS-97 and refined by full-matrix
least-squares analysis.20 The hydrogen atoms were generated
theoretically onto the specific atoms and refined isotropically
with fixed thermal factors. The non-H atoms in 2, 4, and 5 were
refined with anisotropic thermal parameters. There are disor-
dered solvent molecules and anions in the crystal lattice of
compound 5, whose contribution to the structural data was
removed by the SQUEEZE function.21 In 3n the non-H atoms of
solvent molecules are refined isotropically because of low
quality of the sample. The crystal parameters, data collection,
and refinement results for compounds 2, 3n, 4, and 5 are
summarized in Table 1. Selected bond lengths and angles are
listed in Table 2. Further details are provided in the Supporting
Information.
102.7(3)
81.4(3)
4
Cu1-N3
1.998(13)
2.072(11)
1.972(11)
134.5(5)
104.5(5)
79.4(5)
Cu1-N1
2.050(11)
2.124(13)
2.010(10)
104.5(5)
126.0(5)
103.3(5)
90.8(4)
Cu1-N4#4
Cu1-N2
Cu2-N6
Cu2-N5
N3-Cu1-N1
N1-Cu1-N4#4
N1-Cu1-N2
N6#5-Cu2-N5
N3-Cu1-N4#4
N3-Cu1-N2
N4#4-Cu1-N2
N6-Cu2-N5
89.2(4)
5
Cu1-N3#6
1.977(5)
2.070(5)
1.962(4)
2.091(4)
120.4(2)
111.3(2)
112.1(2)
119.2(2)
114.39(19)
108.6(2)
Cu1-N4#7
1.979(5)
2.107(5)
1.980(5)
2.108(4)
114.3(2)
111.2(2)
80.9(2)
111.26(19)
116.44(18)
80.89(18)
Cu1-N1
Cu1-N2
Cu2-N8#8
Cu2-N5
Cu2-N7#9
Cu2-N6
N3#6-Cu1-N4#7
N4#7-Cu1-N1
N4#7-Cu1-N2
N8#8-Cu2-N7#9
N7#9-Cu2-N5
N7#9-Cu2-N6
N3#6-Cu1-N1
N3#6-Cu1-N2
N1-Cu1-N2
N8#8-Cu2-N5
N8#8-Cu2-N6
N5-Cu2-N6
Acknowledgment. We are grateful to the Deutsche
Forschungsgemeinschaft and the University of Siegen for con-
tinued support and are deeply indebted to the Alexander von
Humboldt Stiftung for a AvH stipend for J.F. This manuscript
is dedicated to Prof. Dr. H.-D. Lutz on the occasion of his 75th
birthday.
a Symmetry transformations used to generate equivalent atoms: (#1)
-y, xþ5/2, zþ5/4; (#2) -xþ4, y-1/2, -zþ1; (#3) x, yþ1, z; (#4) x, -
yþ3/2, zþ3/2; (#5) -xþ2, -yþ1, -z-1; (#6) yþ2/3, -xþyþ1/3, -zþ1/
3; (#7) -y, x-y-1, z; (#8) -y, x-y, z; (#9) y, -xþy, -z.
Supporting Information Available: Experimental details, mass
spectra, NMR data, and crystal data. This material is available
free of charge via the Internet at http://pubs.acs.org.
(5.59 mg, 15.0 μmol) were dissolved in a mixture of 1,2-dichloro-
benzene and acetonitrile (10.0 mL, 9:1) to afford a slightly
yellow solution. Then, meso-tetra(4-pyridyl)porphyrin (TPP,
3.09 mg, 5.00 μmol) was added, and the mixture was heated to
reflux for 30 min. The solution was put aside, and after slow
evaporation of acetonitrile, dark red single crystals were ob-
tained. mp: >300 °C; IR (KBr): = ν~ 3438, 2916, 1601, 1543,
1481, 1456, 1415, 1378, 1349, 1325, 1304, 1208, 1137, 1125, 1084,
(20) (a) Sheldrick, G. M. SHELXS97: Program for Crystal Structure
::
::
Determination; University of Gottingen: Gottingen, Germany, 1997. (b) Sheldrick,
G. M. SHELXL97: Program for Crystal Structural Refinement; University of
::
::
Gottingen: Gottingen, Germany, 1997.
(21) (a) Spek, A. L. Acta Crystallogr. 1990, A46, C34. (b) Spek, A. L.
PLATON,
A Multipurpose Crystallographic Tool; Ultrecht University:
Ultrecht, The Netherlands, 2006.