Coordination-driven hierarchical organization of π-conjugated systems: From molecular to supramolecular π-stacked assemblies

Article abstract of DOI:10.1002/chem.201000621

The reaction of U-shaped, bimetallic, Cu^I complexes, assembled from a heteroditopic pincer, with cyano-capped π-conjugated linkers gives a straightforward access to πstacked metallocyclophanes in good yields. In these assemblies, the π-walls ha

Full text of DOI:10.1002/chem.201000621

FULL PAPER
DOI: 10.1002/chem.201000621
Coordination-Driven Hierarchical Organization of p-Conjugated Systems:
From Molecular to Supramolecular p-Stacked Assemblies
Yishan Yao, Wenting Shen, Brigitte Nohra, Christophe Lescop,* and Rꢀgis Rꢀau*[a]
Abstract: The reaction of U-shaped, bi-
different chemical compositions (oli-
go(para-phenylenevinylene)s OPVs,
oligo(phenylene)s, oligo(phenylethynyl-
ene)s), and alternative geometries
(linear, angular). Linkers that incorpo-
rate an internal pyridyne moiety can
also be employed. X-ray diffraction
studies revealed that the metallocyclo-
phanes based on linear linkers self-or-
ganize into infinite p-stacked columns
in the solid state with intermolecular
distances of about 3.6 ꢁ. This ap-
proach, based on coordination-driven
self-assembly, provides a novel and ra-
tional strategy for the stacking of ex-
tended p-systems in the solid state.
metallic, CuI complexes, assembled
from
a
heteroditopic pincer, with
ACHTUNGTRENNUNG
cyano-capped p-conjugated linkers
gives a straightforward access to p-
stacked metallocyclophanes in good
yields. In these assemblies, the p-walls
have an almost face-to-face arrange-
ment. The versatility of this rational
supramolecular synthesis is demon-
strated with the use of linkers that
have nanoscale lengths (up to 27.7 ꢁ),
ACHTUNGTRENNUNG
Keywords: coordination chemistry ·
conjugation · copper · phosphorus
heterocycles
chemistry
·
supramolecular
Introduction
the charge-carrier mobility,[4] a key property for the manu-
facture of efficient organic field effect transistors (OFETs).
In order to tailor the supramolecular organization of p-con-
jugated systems, noncovalent, weak, secondary forces, such
as p–p interactions,[5] hydrogen-bonding,[6] amphiphilic[7] or
charge-transfer[8] interactions, and coordination bonds,[9]
have been utilized. However, each of these different strat-
egies necessitates sophisticated molecular engineering of the
organic p systems and a case-by-case basis. Consequently,
there is a considerable interest to devise fast, reliable, and
general supramolecular approaches to obtain long-range p-
stacking of conjugated systems. Within this area, the control
of the hierarchical organization steps from an isolated mole-
cule in solution to a p-stacked material remains a major
challenge. Breaking this down, it is clear that the most basic
element of this hierarchical process is the formation of p
dimers. With this in mind, a fruitful molecular approach con-
sists of investigating the local control of cofacial p–p inter-
actions of two chromophores into well-defined covalent
scaffolds such as [2,2]-paracyclophanes.[10] These derivatives
have been the subject of unabated interest, since the synthe-
sis of the parent molecule A (Figure 1) in 1949 and Cramꢀs
pioneering studies in the early 1950s.[11] Their structure con-
sists of two p systems that are not directly connected, but
are held parallel to one another in close proximity (ca. 3.1–
3.4 ꢁ). This structure is unique, since benzene, like other
small conjugated p systems (naphthalene, thiophene, oligo-
In recent years, significant scientific interest combined with
a major technological effort has been devoted to the use of
p-conjugated systems as advanced materials for the develop-
ment of new electronic devices (light-emitting diodes, field-
effect transistors, photovoltaic cells, and so forth) with en-
hanced physical properties, low-energy consumption, and
ease of manufacture in agreement with the development of
a sustainable economy.[1] One of the most critical issues de-
termining the performance of these types of device is the
extent of long-range (micrometer regime) supramolecular
organization of the p-conjugated components (oligomers
and polymers)[1h,2] in the solid state, since intermolecular in-
teractions alter physical properties of the bulk material.[3]
For example, it is well established that long-range intermo-
lecular p overlap between the conjugated systems increases
[a] Dr. Y. Yao, W. Shen, Dr. B. Nohra, Dr. C. Lescop, Prof. R. Rꢂau
Sciences Chimiques de Rennes
UMR 6226 CNRS-Universitꢂ de Rennes 1
Campus de Beaulieu, 35042 Rennes Cedex (France)
Fax : (+33)2-23-23-69-39
E-mail: regis.reau@univ-rennes1.fr
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201000621.
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7143

p-stacked [2.2]-paracyclophane analogues B (Figure 1, inter-
planar distance ca. 3.6 ꢁ) are still rare (vide supra). Further-
more, no bimetallic molecular clip that allows a systematic
variation of the length, structure, and geometry of the p
linkers in order to create a structural diversity in p-stacked
supramolecules B has been reported so far.
Figure 1. ACHTUNGTRENNUNG[2.2]Paracyclophane A and supramolecular analogues B.
In this paper, we describe a general and versatile coordi-
nation-driven synthetic method for the preparation of p-
stacked [2,2]-paracyclophane analogues B (Figure 1). This
self-assembly strategy, based on unique, U-shaped, bimetal-
lic CuI-complexes, allows an unprecedented structural varia-
tion of the p core with the incorporation of known conjugat-
ed p systems (oligo(para-phenylenevinylene)s OPVs[22] and
oligo(phenylene)s,[23] oligo(phenylethynylene)s),[24] which
are widely used for (opto)electronic applications. The versa-
tility of this supramolecular synthetic method towards as-
semblies B relies not only on the ease of the p-core varia-
tion, but also on the modification of their length (varying
from 2.7 to 22.6 ꢁ)[25] and of their geometry (linear, angu-
lar). Moreover, it will be shown that the supramolecular as-
semblies B based on linear p connectors self-organize into
infinite p-stacked columns in the solid state.[26] This coordi-
nation-driven long-range hierarchical organization of p-con-
jugated oligomers is unprecedented and its generality opens
appealing perspectives for the design of advanced materials.
ACHTUNGTRENNUNG
(phenylenevinylene)s, etc.),[5a,12] prefers T-shaped edge-to-
face or parallel-displaced interaction geometries in the solid
state. Therefore, [2.2]-paracyclophanes are layered p-conju-
gated molecules par excellence.
After a long period of basic research devoted to the study
of the intriguing interaction between the stacked p systems
(three-dimensional aromaticity) and the resulting impact on
their photophysical and chemical behavior,[13] [2.2]-paracy-
clophane-based derivatives have been gaining practical im-
portance in numerous areas, such as materials science (pre-
cursors of insulating thin films[14] or semiconducting organic
materials[15]), organometallic chemistry (ligand design),[16]
supramolecular chemistry, and nano chemistry.[17] It is strik-
ing to note that methods of derivatization of the [2.2]-para-
cyclophane scaffold for these applications have almost ex-
clusively involved the incorporation of lateral substituents
on the benzene moieties of the parent compound
A
(Figure 1).[10,18] In this context, the development of a versa-
tile and simple strategy to vary the p core of molecular
[2.2]-paracyclophane derivatives and to readily generate a
structural diversity by modifying the nature (length, consti-
tution, topology, etc.) of their stacked p systems is of great
interest.
Results and Discussion
To build supramolecular analogues B of the [2.2]-paracyclo-
phane A, two different synthetic approaches based on either
the design of the p-conjugated walls (tailoring of L moieties,
Figure 1) or of the metal/hydrogen-bond donor nodes have
been reported. The first involves the modification of the p
walls by heteroditopic chelating moieties (2-(phosphino)-
It is hard to envisage the step-wise organic synthetic pro-
cedures that are readily accessible for the extensive diversi-
fication of the [2.2]-paracyclophane p core, since they are
time- and yield-prohibitive and involve the need to over-
come many synthetic challenges. An appealing alternative
to classic synthetic methodologies for constructing complex
molecules is the application of synthetic self-assembly.[9a,b,19]
This powerful approach is based on the spontaneous assem-
bly of rationally designed and preprogrammed individual
building blocks into well-defined supramolecular architec-
tures. Such a process involves noncovalent, kinetically labile,
bond formation (hydrogen bonding, p–p interactions,
metal–ligand coordination, etc.) such that, under proper syn-
thetic conditions, the assemblages undergo self-sorting and
self-correction processes until the individual building blocks
congregate into the final target product. The retrosynthetic
analysis for such a strategy is based on the overall shape of
the desired assembly and the symmetry of the linking sites
of the individual building blocks (directional-bonding ap-
proach).[20] In the last decades this powerful, rational ap-
proach has been used for the synthesis of a large variety of
polygons by means of the assembly of organic multitopic p-
conjugated linkers and metal centers.[21] It is important to
note that, amongst the numerous supramolecular rectangles
incorporating p-conjugated walls that have been reported,
AHCTUNGTRENNUNG
ethoxy, 2-(phosphino)thioethoxy,[27] or oxamate)[28] in order
to obtain linkers that will coordinate to metal centers to
give assemblies of type C and D (Figure 2a). The second ap-
proach relies on the synthesis of bimetallic molecular clips
programmed to assemble homoditopic p systems into supra-
molecules following the concepts of the “directional-bond-
ing approach”.[20a,b] According to this rational approach, the
construction of metalloparacyclophanes B with p-stacked
walls requires a molecular clip with a “U-shaped” geometry
(two cis coordinatively labile sites) and a short intermetallic
distance (ca. below 3.5 ꢁ). Bimetallic complexes satisfying
these criteria that have been used to construct p-stacked as-
semblies B and that have been characterized by X-ray dif-
fraction study are scarce.
To the best of our knowledge, only the ReI dimers F (as-
sembled by hydroxo, alkoxo, or sulfide ligands),[29] the ZnII
dimer G (bridged by two m-O atoms),[30] and the AgI- or
AuI-dimers H (based on diphosphine ligands),[31] afforded p-
stacked supramolecular rectangles of type B (p–p distances,
3.6–3.7 ꢁ) through the reaction with 4-pyridine-capped p
systems (Figure 2b). Other peculiar examples affording
“collapsed molecular rectangles” based on ReI dimers
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Supramolecular Chemistry
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Figure 3. Synthesis of p-stacked supramolecular assemblies of type B by
using hydrogen-bond donors.
tems that has been incorporated into assemblies B is rather
limited (Figures 2 and 3).
Structure of the molecular CuI-clips 2a,b and synthesis of
the homoditopic connectors 3–13: Bis(2-pyridyl)phosphole
derivative 1[34] (Scheme 1) has recently emerged as a useful
assembling N,P,N-pincer for the stabilization of bimetallic
complexes, including metals with different coordination ge-
Figure 2. Synthesis of p-stacked supramolecular assemblies of type B
using a) heteroditopic chelating moieties and b) U-shaped bimetallic mo-
lecular clips.
etries (PdI, PtI, CuI, AgI).[35,36] In these dimers, the P
ACHUTNGRENoNUG mACHTUNGTRENNUGN
bridged by bipyrimidine and bis-(benzimisazolate) ligands
have also been structurally characterized.[32]
Only one approach towards architecture B based on hy-
drogen bonding has been investigated to date, with the co-
atom of 1 adopts either a semi- or a symmetrical-bridging
coordination mode, something that is very rare for s3,l3-R3P
phosphorus donors.[37] Among these bimetallic complexes,
CuI derivatives 2a,b[35] (Scheme 1) possess two available
“cisoid” coordination sites (occupied by kinetically labile
acetonitrile ligands) and, as a consequence of the bridging
phosphane coordination mode, short metal–metal distances
ACHTUNGTRENNUNGcrystallization of (4-pyridyl)-capped p-systems with resorci-
nol template I1 or 1,8-naphthalenedicarboxylic acid template
I2 (Figure 3).[6g,33] The resulting assemblies are held together
ꢀ
by four O H···N hydrogen bonds and the p systems have a
(dACTHUNGTERNNU(G Cu-Cu); 2a: 2.551(1) ꢁ; 2b: 2.667(1) ꢁ). Thus, bimetallic
face-to-face arrangement (p–p distances, ca. 3.7–3.8 ꢁ). It is
worth noting that among all the supramolecular p-stacked
assemblies B depicted in Figures 2 and 3, only the species
based on hydrogen donor I1 and the anthracenyl or thienyl
p linkers (Figure 3) aggregate into infinite p-stacked col-
umns in the solid state.[33e]
CuI complexes 2a,b possess a constrained U-shaped geome-
try and are therefore potential molecular clips for the coor-
dination-driven self-assembly of ditopic p-conjugated sys-
tems into p-stacked metallocyclophanes B (Figure 1). It is
worth noting that the intermetallic distances in complexes
2a,b are markedly shorter than those of dimers F[29] (ca.
3.8 ꢁ), G[30] (ca. 3.6 ꢁ), and H[31] (3.15 ꢁ), which have al-
ready been used to prepare supramolecules B (Figure 2). In
addition, the metal–metal distances in dimers 2a,b are ex-
pected to be fixed, since the CuI2 cores are assembled both
by a tri- (derivative 1) and a bidentate (derivative 1 or 1,2-
bis(diphenylphosphino)methane, abbreviated as dppm) lig-
These examples validate the use of the directional-bond-
ing approach based on the design of programmed U-shaped
clips for the synthesis of p-stacked [2.2]-paracyclophane an-
alogues B. However, two important limitations have to be
noted. Firstly, all the examples reported to date involve the
use of 4-pyridyl moieties as coordination termini. The pres-
ence of this aromatic heterocycle influences the electronic
properties (HOMO and LUMO levels) of the investigated
p-conjugated systems, an effect that is even more pro-
nounced upon coordination to metal centers in assemblies B
(Figures 2 and 3).[20c] Secondly, the structural diversity in
terms of chemical composition and geometry of the p sys-
AHCTUNGTREGaNNUN nds. These properties make derivatives 2a,b appealing clip
structures to enforce stacking of the p walls within assem-
blies of type B. Another key feature of these CuI dimers is
that they are readily accessible on gram scales and that they
are easy to handle due to their air-stability and good solubil-
ity in conventional polar solvents (CH2Cl2, THF…).
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R. Rꢂau, C. Lescop et al.
Scheme 1.
To build p-stacked metallocyclophanes of type
B
297 nm, loge=3.1),[39] confirming that the cyano-termini
have little influence on the electronic properties of these p-
conjugated systems.
(Figure 1) using CuI dimers 2a,b, cyano-capped organic con-
I
ꢀ
ꢁ
nectors were selected since 1) the Cu
A
modynamically stable, but kinetically labile, two important
properties for coordination-driven self-assembly synthesis,
and 2) the presence of the cyano-termini is expected to per-
turb the electronic properties of the p-conjugated systems
only to a lesser extent. Derivatives 3, 4, and 8 (Scheme 1)
are commercially available and compounds 9[38a] and 10[38b]
were prepared according to literature procedures. The novel
homoditopic oligo(para-phenylenevinylene)s (OPVs) 5–7
and 11–12 (Scheme 1), as well as the pyridine derivative 13,
were readily obtained using classic synthetic routes involving
Wadsworth–Emmons reactions (affording only all-trans iso-
mers) between 4-cyanobenzaldehyde and diethyl phosphonic
esters. All new compounds were characterized by multinu-
clear NMR spectroscopy and mass spectrometry. Note that
the absorption maxima of derivative 6 (labs =299 nm, loge=
2.9, Scheme 1) recorded in CH2Cl2 (c=1ꢄ10ꢀ4 molLꢀ1) is
The X-ray structure of cyano-capped OPVs 5 and 6 (see
Experimental Section) were investigated in order to gain in-
sight into their solid-state organization before coordination.
The shorter compound 5 participates in p-stacked arrays
(p-/p distances, ca. 3.5 ꢁ) with a lateral displacement of ap-
proximately 3.1 ꢁ (Figure 4a). Two adjacent p-stacked
arrays develop along parallel axes with a herringbone ar-
rangement. In contrast, the arrangement of the longer OPV
derivative 6 is much more complicated. Four molecules of 6
have a laterally displaced (offset, ca. 1.5 ꢁ) p-stacked ar-
rangement (p–p distances, ca. 3.4 ꢁ), and are surrounded by
four molecules of 6 involved in CH···p interactions (CH···p
distances, ca. 2.8 ꢁ; Figure 4b). These solid-state structures
illustrate, once again,[5a] that face-to-face p-stacking is not a
favored arrangement and that p-conjugated compounds
with the same structural motif, but different lengths (5,
9.4 ꢁ; 6, 16.0 ꢁ),[25] can exhibit very different organization
similar to that of the corresponding parent OPV (labs
=
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Supramolecular Chemistry
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1
1.8 ppm). In addition, the H NMR signals the pyridine lig-
ands of the CuI clips are displaced to higher frequency
AHCTUNGTRENNUNG
(Dd=0.3–0.4 ppm). These coordination shifts, which are due
to the cone effect arising from the presence of two anthra-
cene moieties in derivative 14a, are diagnostic of the pres-
ence of the metallacycle 14a in solution and are fully consis-
tent with p–p interaction between the two ditopic connec-
tors within the targeted self-assembled metallocyclophanes.
The definite proof for the proposed structures was given
by single X-ray diffraction studies. Single crystals of deriva-
tives 14a,b and 15a,b were obtained at room temperature
from pentane diffusion into solutions of the complexes in
CH2Cl2 (see Experimental Section). All derivatives afforded
Figure 4. Solid-state organization of cyano-capped OPV 5 (a) and 6 (b).
¯
homogeneous batches of crystals, which crystallize in the P1
in the solid state. This structure dependence, which is due to
the maximization of dispersive and minimization of repul-
sive interactions, prevents a priori prediction the solid-state
organization of these organic p systems from their molecu-
lar structures.
space group of the triclinic system. The asymmetric unit
cells of 14a,b and 15a,b contain half a rectangle, two PF6
ꢀ
ions and various numbers of CH2Cl2 solvent molecules, the
entire supramolecular assemblies being generated through
an inversion center (Figure 5a). Derivatives 14a,b and 15a,b
are metallacycles of type B (Figure 1) resulting from the co-
ordination of the homoditopic connectors 3 and 4, respec-
tively, to the molecular clips 2a,b, respectively All counter-
ions and cocrystallized solvent molecules are located outside
the self-assembled structures. Whatever the nature of the
molecular clips, the four CuI centers of the supramolecular
assemblies lie in the same plane defining a rectangle (Fig-
ure 5b). The metric parameters of the dicationic CuI2(1)2
General synthetic strategy and solid-state structures of short
(p-wall lengths <3 ꢁ)[25] p-stacked metallocyclophanes:
Complexes 2a,b were first reacted in CH2Cl2 at 408C with
anthracene-9,10-carbonitrile (3) and 1,4-dicyanobenzene (4,
Scheme 1) in order to check their ability to act as molecular
clips for the self-assembly of cyano-capped conjugated sys-
tems into p-stacked metallocyclophanes. The resulting as-
semblies 14a,b and 15a,b (Scheme 1) were isolated in good
yields (ca. 60–70%) upon crystallization from pentane diffu-
sion into the reaction solutions. These supramolecular as-
semblies are isolated as air-stable powders that are soluble
in common polar solvents (acetone, THF, CH2Cl2, etc.)
except for derivative 14b, which is poorly soluble in CH2Cl2.
Elemental analyses support the proposed structures. The
31P{1H} NMR spectra of assemblies 14a,b and 15a,b
(Table 1) display signals with chemical shifts and multiplici-
ties that are similar to those of the corresponding free mo-
lecular clips 2a,b.[35] These data indicate that the molecular
structures of the CuI dimers featuring bridging P centers are
maintained in the supramolecular assemblies. The room-
and CuI2(1)
15a,b,respectively, including the metal–metal and metal–mP
ACHTUNGTRENUN(NG dppm) cores of the metallacycles 14a,b and
ꢁ
ꢀ
ꢀ
ꢀ
ꢁ
distances or the directing (-C N) Cu Cu ACTHUNRTGNEUNG(N C-) angles,
are very similar to those of the corresponding molecular
clips 2a,b (Table 2). The Cu–cyano bond lengths are typical
ꢀ
ꢁ
(1.98–2.09 ꢁ), while the Cu ACTHNUTRGNEUGN(N C-) angles vary from 1658
to 1808 (Figure 3b), revealing little steric stress within the
metallacycles.
In all compounds, the benzene and anthracene moieties of
the coordinated linkers are parallel as a result of hindered
rotation (Figure 5). However, these two p walls exhibit dif-
ferent arrangements with respect to the plane defined by
the CuI atoms. The angles between the benzene ring of
linker 4 and the Cu4 plane lie in the same range for both
types of CuI clip (15a, 79.28; 15b, 79.68, Figure 5c). In con-
trast, the corresponding angles associated with the anthra-
cene moieties in assembly 14a and 14b based on CuI2(1)2
1
temperature H NMR spectra of derivatives 14a,b and 15a,b
are fully consistent with their highly symmetrical structures
and with the expected 1:1 (Cu2)-clip/p-connector ratio. In-
1
terestingly, the H NMR spectrum of derivative 14a record-
ed at 213 K shows that the chemical shifts of the protons of
the anthracene moieties are significantly shifted to lower
frequency compared to those of the free linker 3 (Dd=
and CuI2(1)
ACTHUNGTERNNU(G dppm) nodes, respectively, are markedly differ-
ent (14a, 31.78; 14b, 81.48; Figure 5c). In addition, the
phosphole ligands have a different arrangement within the
Table 1. Selected 31P{1H} NMR data recorded in CH2Cl2 for molecular clips 2a,b[35] and assemblies 14a,b–17a,b and 18a–24a.
Derivative
d31P [ppm] (2J
N
Derivative
d31P [ppm] (2J
(P,P) [Hz])
Derivative
d31P [ppm] (2J
ACHTUNGTRENNUNG(P,P) [Hz])
2a
2b
14a
14b
15a
15b
8.9 (brs)
16a
16b
17a
17b
18a
19a
8.7 (brm)
20a
21a
22a
23a
24a
6.8 (brs)
7.9 (brs)
7.8 (brs)
7.7 (brs)
7.5 (brs)
ꢀ1.6 (brs), 13.7 (brs, m-P)
ꢀ3.4 (d, 84), 12.8 (t, 84)
3.2 (brs)
8.7 (brs)
ꢀ1.2 (brs), 14.5 (brs, m-P)
7.2 (brm)
3.2 (brs), 13.3 (t, 79.6, m-P)
0.4 (d, 72.9), 16.5 (t, 72.9)
7.5 (brs)
8.9 (brs)
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R. Rꢂau, C. Lescop et al.
Figure 5. a) X-ray crystal structures of 14a,b and 15a,b (H atoms, counterions and solvents have been omitted for clarity). b) Views along the long sides
of the Cu4 rectangles. c) Views along the short sides of the Cu4 rectangles.
two metallacycles 14a and 15a with anthracene- and ben-
zene-based walls, respectively. As observed in the free mo-
lecular clip 2a,[35] the P-phenyl substituents of the bridging P
donors point towards the cyano ligands in assembly 15a,
whereas in assembly 14a they point in the opposite direction
(Figure 5a).
more pronounced for the CuI2(1)2 than for the CuI2(1)-
(dppm) clips (Table 3), and in this latter case the p systems
AHCTUNGTRENNUNG
have a face-to-face arrangement (Figure 5b,c). Therefore,
supramolecules 14a,b and 15a,b mimic the spatial organiza-
tion that is encountered in the [2,2]-paracyclophane struc-
ture A (Figure 1). As anticipated from their U-shaped struc-
ture, molecular dimers 2a,b are versatile molecular clips for
the coordination-driven self-assembly of p-stacked metallo-
cyclophanes upon reaction with linear ditopic chromo-
phores. Thermodynamically disfavored face-to-face arrange-
ments of symmetrical p-linkers can be obtained easily using
these rigid bimetallic CuI2 nodes.
It is known that the bimetallic complex 2a (Scheme 1) ex-
hibits fluxional behavior in solution due to the hemilability
of the N,P,N ligand 1 (intramolecular exchange between the
pendant and coordinated pyridiyl groups resulting in inter-
conversion of the P atoms),[35b,40] and it is very likely that
this re-organization of the phosphole ligand within the
[CuI2(1)2]2+ cores during the supramolecular synthetic pro-
cess is driven by steric strain minimization. It is therefore
important to note that, compared to the other U-shaped bi-
metallic molecular clips F–H previously used (Figure 2),
dimer 2a exhibits different behavior since its CuI2(1)2 core
can adapt its ligand conformation to satisfy the specific
steric demand of the p-conjugated linkers, while keeping its
rigid U-shaped topology (Figure 5). In spite of these differ-
ent arrangements, all p walls of the connectors within the
metallacycles 14a,b and 15a,b participate to p stacking (p–p
distances: 3.4–3.5 ꢁ). The lateral offset of the parallel p sys-
tems depends on the nature of the molecular clips. They are
Characterization of nanoscopic (p-wall lengths >3 ꢁ)[25] p-
stacked metallocyclophanes based on OPV-based ditopic
connectors: To evaluate the connector size limit in the coor-
dination-driven self-assembly process towards p-stacked
metallocyclophanes B, we have investigated the use of oligo-
phenylvinylene (OPV) linkers 5–7 with increasing lengths
(Scheme 1). OPVs were selected since they are among the
most widely investigated organic materials for optoelectron-
ic applications (organic light emitting diodes, photovoltaic
cells, etc.).[22] The reaction of molecular clips 2a,b with de-
rivatives 5 and 6 in CH2Cl2 at 408C for 15 h afforded the
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Supramolecular Chemistry
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Table 2. Selected bond lengths [ꢁ], angles [8] and torsion angle of the Cu
14a,b–16a,b1,2 and 17a–24a.
(Nm-PN) moieties of molecular clips 2a,b[35] and supramolecular assemblies
2ACHTUNGTRENNUNG
ꢀ
ꢀ
Cu N
ꢀ
Cu mP
Cu Cu
N-Cu-mP
Cu-mP-Cu
mP-Cu-Cu
Cu-NC-
CN-Cu-Cu-NC
34.1
2a
2.293(1)
2.048(4)
2.043(4)
2.057(2)
2.061(2)
2.096(4)
2.037(4)
2.058(3)
2.074(3)
2.052(3)
2.049(3)
2.058(6)
2.057(5)
2.077(3)
2.061(3)
2.040(5)
2.065(5)
2.062(6)
2.067(6)
2.102(7)
2.048(7)
2.081(8)
2.052(8)
2.086(6)
2.117(7)
2.040(4)
2.070(4)
2.036(6)
2.034(7)
2.032(6)
2.029(6)
2.069(6)
2.057(6)
2.050(4)
2.056(4)
2.075(6)
1.985(6)
2.031(6)
2.071(7)
2.042(4)
2.023(5)
2.064(6)
2.036(5)
2.5552(8)
2.6696(7)
2.5622(10)
2.7446(11)
2.6117(9)
2.6851(14)
2.6294(6)
2.6826(12)
2.7228(13)
2.740(5)
86.14(1)
82.85(1)
85.80(7)
82.78(7)
81.10(11)
84.46(11)
82.31(9)
80.74(9)
84.24(9)
84.44(9)
85.97(17)
83.97(16)
83.87(9)
85.94(10)
84.02(16)
81.42(15)
83.64(17)
81.02(17)
85.2(3)
79.8(2)
82.4(3)
84.3(2)
85.90(18)
85.9(2)
83.99(11)
85.93(15)
85.3(2)
85.32(19)
85.06(15)
85.32(18)
84.38(15)
84.13(17)
84.95(11)
83.53(11)
85.37(19)
85.86(17)
84.26(18)
85.71(18)
84.50(15)
83.83(11)
85.03(14)
83.40(19)
66.15(4)
55.17(3)
58.68(3)
60.56(2)
52.248(19)
58.23(4)
55.62(3)
55.05(3)
56.60(3)
57.77(3)
54.41(2)
58.97(5)
53.16(5)
53.87(3)
57.92(3)
57.89(5)
54.73(5)
57.34(5)
54.07(5)
59.25(16)
52.46(9)
54.28(16)
55.70(11)
53.79(6)
58.22(8)
54.60(4)
58.07(4)
55.39(5)
57.44(6)
55.21(5)
57.36(5)
53.93(5)
58.43(5)
58.09(4)
55.47(3)
56.45(5)
55.64(5)
53.91(5)
58.35(6)
55.35(3)
57.38(4)
57.81(6)
55.11(4)
1.980(4)
2.042(4)
2.018(2)
2.014(3)
2.035(4)
2.042(4)
1.976(3)
1.979(3)
2.089(3)
1.998(3)
2.005(6)
2.003(6)
1.997(3)
2.058(4)
1.982(6)
1.976(6)
1.975(6)
1.969(6)
2.001(8)
1.991(8)
1.957(9)
1.968(8)
2.028(6)
2.058(6)
2.002(4)
2.040(5)
1.921(8)
2.065(8)
1.978(6)
2.055(6)
1.961(6)
2.024(6)
2.035(4)
2.004(4)
2.075(6)
2.041(6)
1.983(5)
2.069(6)
1.984(5)
2.023(5)
1.967(7)
1.947(8)
2.386(1)
2b
2.2898(8)
2.5221(8)
2.3118(13)
2.3815(13)
2.4655(12)
2.4206(11)
2.2935(10)
2.3858(11)
2.3196(18)
2.4838(19)
2.3994(11)
2.2871(11)
2.3725(19)
2.4615(19)
2.368(2)
2.462(2)
2.339(5)
2.535(7)
2.444(6)
2.402(6)
2.440(3)
2.315(3)
2.2987(16)
2.3932(14)
2.347(2)
2.291(2)
2.3659(19)
2.307(2)
2.4045(19)
2.281(2)
2.3128(13)
2.3831(13)
2.328(2)
67.19(2)
66.16(3)
68.34(4)
67.82(3)
67.87(5)
68.21(3)
67.38(6)
68.60(6)
68.28(18)
70.02(15)
67.99(8)
67.33(5)
67.17(6)
67.44(6)
67.64(6)
66.45(3)
67.91(5)
67.74(6)
67.27(4)
67.08(6)
5.7
36.0
10.5
28.0
7.2
14a
14b
15a
15b1
16a
16b1[a]
27.0
18.5
19.2
14.3
16.0
30.0
28.7
33.3
30.6
30.2
28.7
35.6
33.8
26.0
30.1
16b2[a]
2.780(5)
17a
2.661(2)
18a
2.6019(12)
2.5659(13)
2.5947(12)
2.6100(12)
2.5736(9)
2.6131(12)
2.6121(14)
2.5820(9)
2.5539(11)
19a
20a[b]
21a
22a[a]
2.3502(19)
2.403(2)
2.2809(19)
2.3578(17)
2.3028(13)
2.2745(17)
2.347(2)
23a
24a
[a] Non-centrosymmetric supramolecular assemblies. [b] Two independent supramolecular rectangles are present in the unit cell.
novel derivatives 16a,b and 17a,b, respectively (Scheme 1).
These compounds were isolated as air-stable powders fol-
lowing filtration of the crude reaction mixture and crystalli-
zation by pentane diffusion into solutions of the complexes
in CH2Cl2 (60–70% yields). Elemental analyses and multi-
nuclear NMR spectroscopy are in accordance with the pro-
posed structures and single crystals suitable for X-ray dif-
fraction studies (see Experimental Section) were obtained
for compounds 16a,b1,2 (crystallization of assembly 16b af-
forded crystals of two isomers, namely 16b1 and 16b2) and
17a.
As observed for supramolecular assemblies 14a,b and
15a,b, these compounds have a general structure of type B
that mimics the [2,2]-paracyclophane skeleton (Figure 6a),
except 16b2 in which the four CuI atoms are not in the same
plane (Cu-Cu-Cu-Cu dihedral angle, 73.48; Figure 6b). It is
interesting to note that the metallacyclophanes 16a and 17a
featuring the CuI2(1)2 moieties are obtained as single dia-
AHCTUNGTREGsNNNU tereoisomers. Their m-P atoms have a mutual anti-position
with respect to the metallacycles with the P-phenyl substitu-
ents pointing towards the cyano-ligands (Figure 6b, deriva-
tives 16a and 17a), an arrangement already observed in rec-
tangle 15a based on 1,4-dicyanobenzene linker (vide supra,
Figure 5). In contrast, assembly 16b based on the molecular
clip 2b is obtained as a mixture of diastereoisomers in the
solid state: one centrosymmetric rectangle and one non-cen-
trosymmetric twisted-ribbon in which the two m-P centers
adopt either an anti- (16b1, Figure 6) or syn-arrangement
(16b2, Figure 6) with respect to the metallacycle.
These results clearly show that [CuI2(1)2]2+ dimer 2a is
ACTHNUTRGNEUNG
more attractive than [CuI2(1)(dppm)]2+ 2b as a molecular
clip for the synthesis of metallacyclophanes, since it affords
Chem. Eur. J. 2010, 16, 7143 – 7163
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7149

R. Rꢂau, C. Lescop et al.
Table 3. Selected lengths [ꢁ] and angles [8] of the supramolecular assemblies 14a,b–16a,b1,2 and 17a–24a.
Cu–Cu long Overall Angle between the Lateral offsets Intramolecular Intermolecular
18a is the longest supramolec-
ular rectangle described to
date, with an intermetallic long
distance of 31.5 ꢁ and a maxi-
mum overall dimension of
46.6 ꢁ.
The solid-state characteriza-
tion of derivatives 16a–18a
gives the unique opportunity to
distance [ꢁ] length [ꢁ] mean planes of the of p walls [ꢁ] p–p distance [ꢁ] p–p distance [ꢁ]
p walls and the
CuI4 rectangle [8]
14a
14b
15a
15b
16a
11.7
11.8
11.8
11.8
18.3
24.4
26.0
25.3
25.5
32.3
31.0
31.7
81.4
79.2
79.6
49.3
87.2
1.8
0.5
1.4
0.4
1.3
1.1
3.4
3.4
3.4
3.5
3.3
3.4
–
–
–
–
3.5
3.8
16b1[a] 18.1
18.2
compare
the
organization
within metallocyclophanes of
OPV-based p walls with lengths
varying from 9.4 to 22.6 ꢁ.[25] In
all cases, including the giant de-
rivatives 17a and 18a, the p
walls are parallel with short in-
16b2[a] 18.2
18.3
32.7
–
1.4
3.3
3.4
17a
18a
25.2
31.5
39.3
46.5
29.7
47.1
58.0
–
1.4–2.0[d]
1.3–2.2[d]
0.9
3.4
3.4
3.7
3.2
3.1
–
19a[b] 15.5
15.7
20a[c] 24.4
24.4
39.6
39.5
38.7
28.2
69.6
57.3
42.1
–
0.5
3.4
3.5
tramolecular distances
(ca.
21a
25.4
1.2
2.3
3.4
3.4
3.3
2.9
3.5 ꢁ, Table 3) indicating that
they are forced to participate in
p–p interactions upon their in-
22a[a] 14.9
16.5
23a
24a
20.0
19.9
33.8
33.6
–
–
2.5
2.5
3.7
3.6
–
–
tegration into these supra-
molecular metallocyclophanes
(Figure 6). Furthermore, in
[a] These supramolecular assemblies are non-centrosymmetric. [b] Twisted-ribbon geometry. [c] Two indepen-
ACHTUNGTRENNUNGdent supramolecular rectangles in the unit cell. [d] Several configurations of the p-systems are observed in the
solid state for these assemblies.
these nanosize assemblies, the p
walls have an almost a face-to-
face arrangement (Figure 6b,
these target supramolecules as single diastereoisomers. The
fluxional coordination behavior (hemilability) of the hetero-
topic ligand 1[35b,40] is very probably a key to this stereoselec-
tive supramolecular synthesis. It is very striking that the
four metallacyclophanes 14a–17a based on the CuI2(1)2 core
are centrosymmetric diastereomers in spite of the fact that
the CuI2(1)2 moieties themselves are non-symmetric, featur-
ing one P,N-chelate (Figure 5 and Figure 6). This result
shows that the centrosymmetric assemblies are very proba-
bly the most energetically favored arrangement amongst the
numerous possible diastereomers. This high selectivity is a
major advantage both for characterization purposes and for
development of new materials for optoelectronic applica-
tions. Therefore, only the molecular clip 2a was used in the
following self-assembly experiments.
Table 3). These results highlight that CuI dimer 2a is a ver-
satile molecular clip for the construction of ditopic OPV
oligomers within supramolecular p-stacked assemblies
having a [2,2]-paracyclophane geometry. They also demon-
strate the simplicity and power of coordination-driven
supramolecular synthesis to prepare [2,2]-paracyclophane
analogues with unprecedented nanosize lengths.
Variation of the chemical composition and geometry of the
ditopic connectors: To check the scope of this synthetic ap-
proach for the generation of structurally diverse p-stacked
paracyclophanes, p-conjugated linkers with chemical compo-
sitions or geometries other than linear OPVs were investi-
gated. The p systems that have been selected, namely oligo-
AHCTUNGTREG(NNUN phenylene)s and oligo(phenylethynylene)s, are widely in-
To determine whether there is a size limit for the OPV-
based homoditopic connectors in this self-assembly synthe-
sis, dimer 2a was treated for 15 h in CH2Cl2 at 408 with the
poorly soluble OPV-linker 7 (Scheme 1). The resulting clear
red-orange solution shows a 31P{1H} NMR spectrum with a
broad signal at a chemical shift that compares well with
those of assemblies 14a–17a (Table 1). Diffusion of pentane
into the crude reaction solution gave a homogeneous batch
of small red monocrystals (yield, 20%) that were submitted
to X-ray diffraction analyses (see Experimental Section).
Derivative 18a is a supramolecular rectangle (Figure 6b)
with a structure similar to that of the assemblies 16a and
17a (Figure 6). Note that the CuI2(1)2 moieties within supra-
molecule 18a have the conformation found in 15a–17a
(vide infra), confirming that with clip 2a the assembly pro-
cess is highly stereoselective. To the best of our knowledge,
vestigated and useful building blocks for the tailoring of
semiconducting organic materials.[23,24] The molecular clip
2a was reacted at 408C in CH2Cl2 with the cyano-capped
oligophenyl linkers 8 and 9 and with the phenylethynyl-
based connector 10 affording clear red-orange solution of
assemblies 19a, 20a, and 21a, respectively (Scheme 1). They
exhibit solution-state 31P {1H} NMR signals similar to those
recorded for derivatives 14a–18a (Table 3). Red, single crys-
tals suitable for X-ray diffraction studies (see Experimental
Section) were grown upon pentane diffusion into CH2Cl2
solutions (yields: 19a, 65%; 20a, 69%; 21a, 67%). X-ray
structure resolutions revealed that these novel assemblies
are p-stacked metallocyclophanes (Figure 7) with a general
structure of type B. Compounds 20a and 21a are centrosym-
metric rectangles with the four Cu atoms lying within the
same plane (Table 3), whereas the non-centrosymmetric de-
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Supramolecular Chemistry
FULL PAPER
Figure 6. a) X-ray crystal structures of 16a,b1,2, 17a and 18a (H atoms, counterions and solvents have been omitted for clarity); for 16b2, 17a and 18a
the conformational disorder of the connector is not shown, see Supporting Information. b) Views along the long sides of the Cu4 quadrangle. c) Views
along the short sides of the Cu4 quadrangle.
rivative 19a incorporating biphenyl-based linker 8 exhibits a
“twisted ribbon” geometry as a result of the twist angles
mains stereoselective whatever the chemical composition
and the length of the ditopic p connectors.
ꢀ
(328–408) around the central C C bond of 8 (Figure 7b).
The next step to estimate the versatility of our coordina-
tion-driven synthetic approach towards p-stacked metallocy-
clophanes B was to use angular p-ditopic linkers. To date,
only the angular pyridyl-caped p-conjugated homoditopic
connectors J[33e] and K[41] (coordination directional angles
around 1308, Figure 8) have been reacted with the U-shaped
molecular clips I1 (Figure 3) and the PtII dimer L (Figure 8),
respectively, affording supramolecular metallacycles. Note
that due to its long Pt–-Pt distance (ca. 6.4 ꢁ), dimer L
cannot force the homoditopic connectors K to participate in
p–p interactions and the p walls lie in the plane defined by
the four Pt centers.[41] Following our investigation of linear
OPV-based linkers, the angular connectors 11 and 12 with a
1,2- and a 1,3-distyrylbenzene core, respectively, were inves-
tigated (Scheme 1). It should be underlined that the use of
connectors 11 and 12 to construct metallocyclophanes by
Consequently, the axes of the two m-P bridged CuI–CuI
dimers are not parallel and exhibit a torsion angle of 53.98.
This twisted ribbon geometry is not observed in the longer
supramolecular assembly 20a (Figure 7b). Whatever the ge-
ometry of the assemblies 19a–21a, their oligoACHTNUTRGNE(UNG phenyl) and
oligo(phenylethylene)-based p-conjugated walls have an
almost face-to-face arrangement (Figure 7; lateral offset:
19a, 0.9; 20a, 0.5; 21a, 1.2 ꢁ) with short intramolecular con-
tacts (<3.7 ꢁ, Table 3) revealing p–p interactions. To the
best of our knowledge, this is the first example of p-stacked
derivatives of type B incorporating tetraphenyl (20a) and
1,4-(bisphenylethynyl)benzene (21a) walls. It is interesting
to note that the stereochemistry of the CuI2(1)2 moieties in
19a–21a is the same as that observed in the series 15a–18a,
showing that molecular clip 2a the assembly process re-
Chem. Eur. J. 2010, 16, 7143 – 7163
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
7151

R. Rꢂau, C. Lescop et al.
bonding approach,[20] which request the use of rigid connec-
tors.
According to the general procedure used with linear link-
ers, derivatives 11 and 12 were reacted with the molecular
clip 2a at 408C for 15 h in CH2Cl2 (Scheme 1), and pentane
was allowed to diffuse into these solutions. This workup af-
forded homogenous batches of single-crystals of derivatives
22a and 23a (Scheme 1) suitable for X-ray diffraction stud-
ies (see Experimental Section) (yield: 22a, 62%; 23a,
56%). The crystals selected for the X-ray crystal structure
determinations were typical of the bulk and there was no in-
dication of polymorphism. Derivatives 22a and 23a are non-
centrosymmetric, supramolecular metallacycles resulting
from the coordination of two angular linkers to two molecu-
lar clips 2a (Figure 9). In contrast to what is observed with
Figure 7. a) X-ray crystal structures of derivatives 19a, 20a (only one of
the two crystallographically independent molecules of the asymmetric
unit is shown) and 21a (H atoms, counterions and solvents have been
omitted for clarity). b) View showing the geometry of derivatives 19a
and 20a.
Figure 9. a) X-ray crystal structures of 22a–24a (H atoms, counterions
and solvents have been omitted for clarity. b) Views along the short sides
of the Cu4 quadrangles.
linear OPV-based ditopic linkers (Figure 6), the Cu atoms of
derivatives 22a and 23a are not in the same plane (dihedral
angles between the two CuI2 axes: 22a, 72.88; 23a, 65.08;
Figure 9). The two p linkers are located on the same side of
the Cu4 surface (Figure 9), and participate in p–p interac-
tions as indicated by the short interplane distances (22a, ca.
3.3; 23a, 3.6 ꢁ, Table 3) with a “parallel displaced” arrange-
ment (lateral offset, 22a, 2.3; 23a, 2.5 ꢁ, Table 3, Fig-
ure 9b). The coordination directional angles of the ditopic
linkers are very acute (22a, 75.7–79.4; 23a, 104.08; Figure 9)
affording these p-stacked supramolecular [2.2]-paracyclo-
phanes 22a and 23a with an unprecedented topology.
Figure 8. Chemical structure of the angular connectors J and K and of
the PtII molecular clip L; view of three possible conformations of the an-
gular linker 12.
self-assembly is quite challenging since, compared to rigid
linkers J and K (Figure 8), 1) their coordination directional
angles are more acute (<1208) and 2) their structure is flexi-
ble as a consequence of the possible cisoid/transoid confor-
mation of their central core (see Figure 8 for the angular
linker 12). This structural flexibility is, a priori, a major
drawback according to the principle of the directionnal
A general limitation of coordination-driven supramolec-
ular synthesis is that the use of functional linkers is prohibit-
ed due to potential reactivity towards the metallic clips.[20]
To check this point in our approach for the formation of p-
7152
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Chem. Eur. J. 2010, 16, 7143 – 7163

Supramolecular Chemistry
FULL PAPER
stacked [2,2]-paracyclophane analogues, the angular linker
13 with the geometry of connector 12 and bearing a central
pyridine moiety (Scheme 1) was selected. The reaction of 13
with CuI-dimer 2a, according to the general synthetic proce-
dure used to prepare assembly 23a, gave rise to derivative
24a (75% yield, Scheme 1), which was characterized by an
X-ray diffraction study (see Experimental Section). Assem-
bly 24a is a p-stacked metallocyclophane that is isostructur-
al to derivative 23a based on the non-functional linker 12
(Figure 9). The N atoms of the inner pyridine rings are un-
coordinated and point in the same direction with an N···N
distance of about 3.96 ꢁ.
The coordination-driven synthesis of p-stacked assemblies
B with very different structures in terms of chemical compo-
sition, length and geometry of the p walls clearly demon-
strate that CuI dimer 2a is a powerful and unique U-shaped
molecular clip. These large architectures are spontaneously
generated in good yields simply by mixing their component
building blocks in solution at room temperature. This simple
and rational supramolecular approach towards [2,2]-paracy-
clophane analogues B appears to be general as illustrated
with the preparation of striking giant (Figure 6) and banana-
shaped (Figure 9) derivatives that have no precedent in the
literature.
Figure 10. View of the unit cell for derivative 15a; proton atoms of the
CH2Cl2 solvent molecules have been removed for clarity.
molecular arrangement in the solid state (Figure 4). The key
role played by the CuI clips is further demonstrated by the
fact that infinite p-stacked columns are also observed with
the linear linkers 9 and 10 based on tetraphenyl and phenyl-
ethynylene moieties, respectively (20a and 21a, Figure 9). It
is particularly striking that despite using p-conjugated link-
ers with quite different chemical composition (OPV, oligo-
ACHTUNGTRENNUNG[2,2]Metalloparacyclophane stacking pattern in the solid
state: Assemblies B (Figure 1) can be regarded as the first
hierarchical suprastructures towards the self-organization of
p systems into long-range p-stacked columns, a solid-state
packing that is of interest for molecular electronic. It is im-
portant to recall that such packing based on cyclophane sub-
units B has only one precedent in the literature (assemblies
incorporating hydrogen donors I,[1] Figure 3)[33e] and has
never been observed with metallocyclophanes B.
AHCTUNGTREG(NNUN phenyl), oligo(phenylethynylene)), the same general hier-
archical organization is observed upon reaction with the
CuI2-clips 2a,b: first a local face-to-face organization of two
p systems within a metallocyclophane, then an infinite “par-
allel-displaced supramolecular arrangement” of these self-
assembled structures in one direction. This supramolecular
self-organization of p-conjugated oligomers in the solid
state, although discovered by serendipity, seems to have a
general and predictable character. Note that for all deriva-
tives, the infinite p-stacked columns are parallel (see Fig-
ure 12a–c for derivatives 17a, 18a, and 20a, and Supporting
Information for the other derivatives). This arrangement
generates channels that are filled by disordered CH2Cl2 sol-
vent molecules, located in the vicinity of the p-conjugated
The supramolecular metallacycles built on “short” linear
p-conjugated linkers 3, 4, and 8 (Scheme 1) do not exhibit
intermolecular p interaction in the crystalline solid state. As
illustrated with derivative 15a (Figure 10), counterions
ꢀ
(PF6 ) and CH2Cl2 solvent molecules are located between
the tetracationic supramolecular rectangle 15a preventing
any intermolecular interactions between the coordinated p
walls to take place. Remarkably, on increasing the length of
the linear OPV-based linkers (4!5–7, Scheme 1), the p-
stacked metallocyclophanes self-organize in the solid state
into infinite columns, with a parallel displaced arrangement
(16a, 16b1,2, 17a, 18a; Figure 11). The lateral offset within
the columns depends on the nature of the CuI-clip (16a (clip
2a) versus 16b (clip 2b), Figure 11). However, in all cases,
the short intermolecular distances (ca. 3.1–3.5 ꢁ, Table 3)
between the p walls of two neighboring supramolecules re-
veals intermolecular p–p interactions. Dispersion forces
probably drive the unexpected formation of these metallocy-
clophane columnar p stacks, since they are observed for de-
rivatives having extended p-conjugated walls only. Note that
the presence of the CuI clips plays a major role in this supra-
molecular p-stacked organization, since the free cyano-
capped linkers do not systematical exhibit this type of supra-
ꢀ
ꢀ
linkers, and the PF6 or BF4 counterions that stand close to
the dicationic CuI2 clips (Figure 12d for derivative 17a and
Supporting Information for the other derivatives).
In contrast, none of the derivatives 22a–24a based on the
angular connectors 11–13, respectively (Scheme 1), form in-
finite networks of intermolecular p–p interacting molecules.
In the solid state, the supramolecular assembly 22a aggre-
gates into dimers that exhibit parallel displaced p–p interac-
tions (intermolecular distances, ca. 3.0 ꢁ) providing an ex-
ample of a solid-state discrete stack of four aromatic mole-
ꢀ
cules (Figure 13a).[42] In this case, a PF6 counterion is locat-
ed in the concave cavity formed by the assembled angular
connectors 11 (Figure 13b). The isostructural derivatives
23a and 24a are isolated supramolecules in the solid-state
with no intermolecular p contacts (shortest intermolecular
distances between p walls, ca. 10 ꢁ, Figure 14). Therefore,
Chem. Eur. J. 2010, 16, 7143 – 7163
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7153

R. Rꢂau, C. Lescop et al.
Figure 11. “Side” and “lateral” views of the stacking patterns of p-stacked metallocyclophanes 16a, 16b1,2, 17a, 18a, 20a, and 21a observed in single
crystals.
the geometry of the p connectors has a dramatic influence
on the dimensionality of the supramolecular p-stacked
arrays with the formation of infinite stack with linear linkers
(Figure 11) and tow- or fourfold stacks with angular linkers
(Figures 13 and 14). These structure–supramolecular-organi-
zation relationships open interesting perspectives for the de-
velopment of a rational approach towards well-defined dis-
crete or infinite p-stacked organic materials.
clip 2a that result in this versatility are 1) its short interme-
tallic distance, due to the presence of bridging P centers, 2)
its structural rigidity, and 3) the hemilability of its assem-
bling heterotopic N,P,N-ligands. This rational synthetic ap-
proach, based on the concepts of the directional-bonding ap-
proach,[20] gives rise to an easy to perform and unique chem-
ical engineering methodology for the generation of p-
stacked paracyclophane derivatives. The organization of the
linear linkers within p-stacked supramolecules results in the
formation of infinite columns in which all the p-systems
overlap (p–p distances, ca 3.5 ꢁ). Notably, this hierarchical
long-range supramolecular organization of linear p-conju-
gated systems is quite general. Therefore, the use of molecu-
lar clips 2a provides a rational strategy for the stacking of
extended p systems in the solid state, providing a minimal
alteration of their structure (introduction of terminal cyano
moiety), a problem which is a major issue in plastic elec-
tronics.
Conclusion
In summary, we have developed a straightforward and ver-
satile supramolecular synthesis of p-stacked [2,2]-paracyclo-
phane analogues B (Figure 1) based on the use of U-shaped
CuI2 molecular clips and homoditopic cyano-capped conju-
gated linkers. The versatility of CuI-clip 2a for generating
structural diversity has been demonstrated with the use of
linkers that have nanoscale lengths (up to 27.7 ꢁ), different
chemical compositions (oligo(para-phenylenevinylene)s
OPVs, oligo(phenylene)s, oligo(phenylethynylene)s), and al-
ternative geometries (linear, angular). The key properties of
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Chem. Eur. J. 2010, 16, 7143 – 7163

Supramolecular Chemistry
FULL PAPER
Figure 13. a) Supramolecular dimer observed in single crystals of metalla-
ꢀ
cycle 22a. b) Location of a PF6 ion in the pocket defined by the curved
structure of derivative 22a.
Figure 14. Organization of the neighboring metallacycles in the single
crystals of supramolecular assembly 23a.
Experimental Section
All experiments were performed under an atmosphere of dry argon using
standard Schlenk techniques. Commercially available reagents were used
as received without further purification. Solvents were freshly distilled
under argon from sodium/benzophenone (diethyl ether) or from phos-
phorus pentoxide (dichloromethane, acetonitrile).1H, 13C, and 31P NMR
spectra were recorded on Bruker AV300, DPX200, or AV500 spectrome-
ters.1H and13C NMR chemical shifts were reported in parts per million
(ppm) relative to Me4Si as external standard.31P NMR downfield chemi-
cal shifts were expressed with a positive sign, in ppm, relative to external
85% H3PO4. Elemental analyses were performed by the CRMPO, Uni-
versity of Rennes at Rennes France.
Figure 12. View of the columnar stacks of derivatives a) 17a, b) 18a, and
ꢀ
c) 20a, PF6 counterions and disordered CH2Cl2 molecules have been
ꢀ
ꢀ
omitted. d) Location of the PF6 counterions for derivative 17a, PF6
Intermediates 4,4’-bis[(diethoxyphosphoryl)methyl]stilbene P5,[43] 1,2-
bis[(diethoxyphosphoryl)methyl]benzene P6,[44,46] 1,3-bis[(diethoxyphos-
phoryl)methyl]benzene P7[45,46] and 2,6-bis[(diethoxyphosphoryl)methyl]-
pyridine P8,[47] the p-conjugated connectors 9[48] and 10,[49] the ligand 1[34]
counterions are represented as polygons, while the supramolecular rec-
tangles are shown in stick and ball style; disordered CH2Cl2 molecules
have been omitted.
Chem. Eur. J. 2010, 16, 7143 – 7163
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7155

R. Rꢂau, C. Lescop et al.
ꢀ
and the PF6 salts of the molecular clips 2a and 2b[35] were synthesized
ꢀ
according to procedures previously published. The BF4 salt of the mo-
ꢀ
lecular clip 2a was prepared according to the same route than the PF6
salts using [CuACHTUNGTRENNUNG ACHUTNGTRNEN(GUN CH3CN)4]PF6.
(CH3CN)4]BF4 as CuI source instead of [Cu
Synthesis of diethyl 4-cyanobenzylphosphonate (P2): Triethyl phosphite
(2.5 equiv, 2.2 mL, 12.7 mmol) was added to a solution of the 4-(bromo-
methyl)benzonitrile (1 g, 5.1 mmol) in CHCl3 (20 mL). The mixture was
stirred at 608C for 12 h and the solvent was removed under vacuum. The
oily product was washed with pentane and a solid was obtained as a
white hydroscopic powder (1.13 g, 88%). 1H NMR ( 200 MHz, CDCl3):
This mixture was stirred for 1 h at room temperature and then 4-cyano-
benzaldehyde (2 equiv, 0.210 g, 1.6 mmol) was added. This mixture was
stirred for one night at 658C. After addition of water (20 mL) and extrac-
tion with dichloromethane (5ꢄ60 mL), the derivative 7 was obtained as
an air-stable yellow powder (0.156 g, 0.4 mmol, 45%). 1H NMR
(300 MHz, C6D6): d=6.50 (s, 2H; Hg), 6.86–7.01 (m, 4H; Hc and Hd),
7.13–7.22 (m, 8H; He and Hf), 7.34–7.44 ppm (m, 8H; Ha and Hb); HR-
MS (EI): m/z calcd for C32H22N2: 434.1783; found: 434.1758 [M]+; ele-
mental analysis calcd (%) for C32H22N2 (434.53 gmolꢀ1): C 88.45, H 5.10,
N 6.45; found C 88.17, H 4.91, N 6.63.
3
2
d=1.31 (t, J
2H; Ph-CH2-PO
O-CH2-CH3) 7.51 ppm (AB system, nAB =38.1 Hz, 3J
H3 and H4); 13C{1H} NMR (75.46 MHz, CDCl3): d=16.1 (s, O-CH2-CH3),
A
ACHTUNGTREN(NUNG P,H)=22.3 Hz,
A
R
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
1
2
33.2 (d, J
ACHTUNGTRENNUNG(P,C)=137.7 Hz, C6), 62.8 (d, JACHTUNGTRENN(UNG P,C)=6.74 Hz, P-O-CH2-CH3),
111.3 (s, C2), 118.4 (s, C1), 131 (s, C3), 132.6 (s, C4), 138.1 ppm (d,
ACHTUNGTRENNUNG
2J(P,C)=9.0 Hz, C5); 31P{1H} NMR (121.5 MHz, CDCl3): d=25.6 ppm;
HR-MS (EI): m/z calcd for C12H16NO3P: 253.0867; found: 253.0861 [M]+.
Synthesis of the linker (11): Derivative P6 (1.0 g, 2.6 mmol) in THF
(20 mL) was added dropwise to a suspended solution of sodium hydride
(0.26 g, 11 mmol) in THF (100 mL) at 08C. The reaction mixture was
warmed to room temperature and
Synthesis of the linker (5): NaH (5 equiv, 0.117 g, 5 mmol) was added to
a solution of the phosphonate derivative P2 (0.250 g, 0.980 mmol) in
THF (20 mL). This mixture was stirred for 30 min at room temperature
stirred for 12 h. 4-Formylbenzonitrile
P3 (0.75 g, 5.7 mmol) in THF (20 mL)
was added to this solution. The reac-
tion mixture was stirred for 6 h, and
then was filtered on short silica
column. The product was the first to
be eluted and inorganic salt was re-
tained. The volatile materials were re-
moved under vacuum. Compound 11
was recrystallized from THF (10 mL)
and then 4-cyanobenzaldehyde (1 equiv, 0.170 g, 0.980 mmol) was added.
This mixture was stirred for one night at 658C. After addition of water
(20 mL) and extraction with dichloromethane (3ꢄ20 mL), the derivative
5 was obtained as air-stable white needles (0.180 g, 0.781 mmol, 70%).
1H NMR (300 MHz, CD2Cl2): d=7.22 (s, 2H; Hc), 7.66 ppm (AB system,
and was obtained as a light orange
solid (0.43 mg, yield 50%). 1H NMR
(300 MHz, CD2Cl2): d=7.04 (d, 3J
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
nAB =11.3 Hz, 3J(H,H)=8.6 Hz, 4H; Ha and Hb); 13C{1H} NMR
(m, 2H; H10), 7.65 (d, 3J
ACHTUNGTRENNUNG
10H; H3, H4, H9); 13C{1H} NMR (75 MHz, CD2Cl2): d=111.0 (s, C2),
118.9 (s, C1), 126.9 (s, C9), 127.1 (s, C4), 128.7 (s, C10), 129.6 (s, C7), 129.9
(s, C6), 132.6 (s, C3), 135.5 (s, C8), 141.7 ppm (C5); HR-MS (EI): m/z
calcd for C24H16N2: 332.1314; found: 332.1318; elemental analysis calcd
(%) for C24H16N2 (332.40 gmolꢀ1): C 86.72, H 4.85, N 8.43; found C
86.55, H 4.91, N 8.59.
(125.77 MHz, CD2Cl2): d=112.3 (s, C2), 119.5 (s, C1), 127.7 (s, C3), 130.7
(s, C6), 133.1 (s, C4), 141.1 ppm (s, C5); HR-MS (EI): m/z calcd for
C16H10N2: 230.0844; found: 230.0848 [M]+; elemental analysis calcd (%)
for C16H10N2 (230.264 gmolꢀ1): C 83.46, H 4.38, N 12.17; found C 83.61,
H 4.31, N 11.98.
Synthesis of the linker (6): NaH (5 equiv, 0.12 g, 5 mmol) was added to a
solution of the phosphonate derivative P2 (2 equiv, 0.5 g, 2 mmol) in
THF (20 mL). This mixture was stirred for 30 min at room temperature
and then terphtaldehyde (1 equiv, 0.131 g, 1 mmol) was added. This mix-
Synthesis of the linker (12): Derivative P7 (1.0 g, 2.6 mmol) in THF
(20 mL) was added dropwise to a suspended solution of sodium hydride
(0.26 g, 11 mmol) in THF (100 mL) at 08C. The reaction mixture was
ture was stirred for one night at 658C. After addition of water (20 mL)
and extraction with dichloromethane (5ꢄ20 mL), the derivative 6 was
obtained as air-stable yellow needles (0.262 g, 0.788 mmol, 80%).
1H NMR (300 MHz, CD2Cl2): d=7.21 (AB system, nAB =15.6 Hz,
warmed to room temperature and stirred for 12 h. 4-Formylbenzonitrile
P3 (0.75 g, 5.7 mmol) in THF (20 mL) was added to this solution. The re-
action mixture was stirred for 6 h, and then was filtered on short silica
column. The product was the first to be eluted in the front and inorganic
salt was retained. The volatile materials were removed under vacuum.
The derivative 12 was recrystallized from THF (10 mL) and was obtained
as a white solid (0.57 g, yield 66%). 1H NMR (300 MHz, CD2Cl2): d=
3J
system, nAB =13.3 Hz, 3J
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
(125.77 MHz, CD2Cl2): d=112.3 (s, C2), 115.7 (s, C1), 126.3 (s, C9), 127.7
(s, C3), 128.3 (s, C7), 130.7 (s, C6), 133.1 (s, C4), 134.4 (s, C8), 141.1 ppm (s,
C5); HR-MS (EI): m/z calcd for C24H16N2: 332.1314; found: 332.1313
[M]+; elemental analysis calcd (%) for C24H16N2 (332.40 gmolꢀ1): C
86.72, H 4.85, N 8.43; found C 86.63, H 4.71, N 8.68.
7.23 (d, 3J
(H,H)=16.4 Hz, H6), 7.32 (d, 2H; 3J
ACHUTGTNRENNUG CAHTUNGTRENNUNG
7.44–7.49 (m, 1H; H10), 7.55–7.58 (m, 2H; H9), 7.68 (d, 3J
AHCTUNGTRENNUNG
2H; H3), 7.72 (d, 3J
ACHTUNGTRENNUNG
13C{1H} NMR (75 MHz, CD2Cl2): d=110.8 (s, C2), 119.0 (s, C1), 125.4 (s,
C11), 126.9 (s, C9, C4), 127.4 (s, C6), 129.3 (s, C10), 131.7 (s, C7), 132.6 (s,
C3), 137.2 (s, C8), 141.6 ppm (s, C5); HR-MS (EI): m/z calcd for C24H16N2:
Synthesis of the linker (7): NaH (10 equiv, 0.19 g, 8 mmol) was added to
a solution of the derivative P5 (1 equiv, 0.4 g, 0.8 mmol) THF (20 mL).
7156
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Supramolecular Chemistry
FULL PAPER
332.1314; found: 332.1318 [M]+; elemental analysis calcd (%) for
C24H16N2 (332.40 gmolꢀ1): C 86.72, H 4.85, N 8.43; found C 86.71, H 4.69,
N 8.43.
Synthesis of supramolecular assembly (15a): Following the general proce-
dure, the reaction of 2a (0.200 g, 0.16 mmol) with 4 (10 equiv, 0.207 g,
1.62 mmol) afforded 15a as an air-stable red solid (0.133 g, 0.06 mmol,
75% yield). 1H NMR(500 MHz, CD2Cl2): d=2.01 (brs, 8H; C=
CCH2CH2), 2.91 (brs, 6H; C=CCH2), 3.13 (brs, 2H; C=CCH2), 7.18–7.40
Synthesis of the linker (13): Derivative P8 (0.200 g, 0.53 mmol) in THF
(10 mL) was added dropwise to a suspended solution of sodium hydride
(0.52 g, 22 mmol) in THF (10 mL) at 08C. The reaction mixture was
ꢁ
(brm, 28H; H5 Py, o,m,p-Ph), 7.56 (s, 8H; H4 Py), 7.60 (s, 8H; N
CCCH), 7.87 (s, 8H; H3 Py), 8.35 ppm (brs, 8H; H6 Py); 13C{1H} NMR
(300 MHz, CD2Cl2): d=21.0 (s, C=CCH2CH2), 26.5 (s, C=CCH2), 115.9
ꢁ
ꢁ
(CuN CCCH), 116.9 (brs, CuN CCCH), 122.6 (brs, C5 Py), 123.8 (brs,
ꢁ
C3 Py), 129.1 (brs, m-Ph), 130.7 (brs, p-Ph), 131.2 (brs, N CCCH), 132.3
(brs, o-Ph), 138.7 (brs, C4 Py), 149.1 ppm (brs, C6 Py); C2 Py, Ca, Cb, and
ipso-Ph were not observed. 31P{1H} NMR (121.5 MHz, CD2Cl2): d=
ꢀ142.8 (sept, 1J
ACHTUGNTERN(NUNG P,F)=710 Hz, PF6), 7.2 ppm (brm, 2P, n1/2 =115 Hz, P);
elemental analysis calcd (%) for C113H94Cl2Cu4F24N12P8 (15aꢄCH2Cl2;
2648.88 gmolꢀ1): C 51.24, H 3.58, N 6.35; found: C 51.41, H 3.79, N 5.95.
Synthesis of supramolecular assembly (15b): Following the general pro-
cedure, the reaction of 2b (0.200 g, 0.16 mmol) with 1,4-dicyanobenzene
4 (4 equiv, 0.081 g, 0.631 mmol) afforded 15b as an air-stable yellow and
orange solid (0.125 g, 0.054 mmol, 67% yield). 1H NMR (300 MHz,
CD2Cl2): d=1.87–1.96 (m, 4H; C=CH2CH2), 2.05–2.20 (m, 4H; C=
CH2CH2), 2.86–3.00 (m, 4H; C=CCH2), 3.12–3.26 (m, 2H; Hd), 3.28–3.40
(m, 4H; C=CCH2), 3.55–3.68 (m, 2H; Hd), 7.05–7.09 (m, 8H; m-Phdppm),
warmed to room temperature and stirred for 6 h. 4-Formylbenzonitrile
(0.121 g, 0.94 mmol) in THF (10 mL) was added to this solution. The re-
action mixture was stirred for 2 h, and then was filtered on short silica
column. The product was the first to be eluted and inorganic salt was re-
tained. The volatile materials were removed in vacuum. The derivative
13 was recrystallized from EtOH (5 mL) and was obtained as a white
solid (0.070 g, yield 40%). 1H NMR (200 MHz, CD2Cl2): d=7.34 (s, 2H;
H9 Py), 7.35 (AB system, nAB =17.2 Hz, 3J
ACHTUNGTRNEG(UN H,H)=10.8 Hz, 4H; H6,7),
7.14–7.21 (m, 8H; m-Phdppm), 7.30 (t, 3J
(d, 3J
(H,H)=6.61 Hz, 4H; H5 Py), 7.40–7.60 (brm, 30H; o,p-Phdppm
o,p-Ph), 7.79 (s, 8H; Ha), 7.79 (d, 3J
(H,H)=7.60 Hz, 4H; H3 Py), 8.05 (t,
3J(H,H)=6.61, 7.60 Hz, 4H; H4 Py), 8.32 ppm (brs, 4H; H6 Py); 13C{1H}
ACHTUNGTNER(NUNG H,H)=7.03 Hz, 4H; m-Ph), 7.34
7.65–7.69 (m, 8H; H3,4), 7.72 ppm (t, J=6.5 Hz, 1H; H10 Py); 13C{1H}
NMR (75 MHz, CD2Cl2): d=111.8 (s, C2), 119.5 (s, C1), 122.4 (s, C9),
127.9 (s, C4), 131.5 (s, C7), 131.7 (s, C6), 132.8 (s, C3), 137.8 (s, C10), 141.5
(C5), 154.9 ppm (s, C8); HR-MS (EI): m/z calcd for C23H15N3: 333.1266;
found: 333.1254 [M]+; elemental analysis calcd (%) for C23H15N3
(333.39 gmolꢀ1): C 82.86, H 4.54, N 12.60; found C 86.65, H 4.63, N
12.41.
A
,
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
NMR (125.77 MHz, CD2Cl2): d=18.80 (s, C=CCH2CH2), 22.32 (s, C=
CCH2), 34.11 (brs, Cd), 122.63 (s, C5 Py), 124.12 (s, C3 Py), 129.11 (brs,
C
C
Ph), 129.60 (brs, CPh), 131.24 (brs, CPh), 132.02 (brs, CPh), 133.56 (brs,
Ph), 139.03 (s, C4 Py), 151.17 ppm (s, C6 Py); C2 Py, Ca, Cb, and ipso-Ph
were not observed; 31P{1H} NMR (121.5 MHz, CD2Cl2): d=ꢀ145.0 (sept,
General procedure for the synthesis of the supramolecular rectangles: A
solution of the ditopic cyano-based connector in CH2Cl2 (10 mL) was
added to a solution of 2a or 2b in CH2Cl2 (15 mL). This mixture was
stirred for 15 h at 408C and then it was filtered and the volatile materials
were removed under vacuum. The solid residues were washed with Et2O
(3ꢄ10 mL) and the supramolecular complexes were isolated as air-stable
powders. Crystals suitable for X-ray diffraction study were obtained at
room temperature from slow diffusion of pentane into a solution of these
derivatives in CH2Cl2. These batches of crystals were dried under
vacuum at room temperature overnight. Yields indicated correspond to
the materials recovered after such crystallizations and after these materi-
als have been left under vacuum for one night at room temperature.
1J
2J
C
CATHNUGTRNEN(NUG P,F)=706 Hz, PF6), 3.2 (brm, 2P, n1/2 =56.7 Hz, Pdppm), 13.3 ppm (t,
AHCTUNGTRENNUNG
52.59; H 3.49; N 4.12.
Synthesis of supramolecular assembly (16a): Following the general proce-
dure, the reaction of 2a (0.200 g, 0.16 mmol) with 5 (1 equiv, 0.037 g,
0.16 mmol) afforded 16a as an air-stable red solid (0.150 g, 0.54 mmol,
67% yield).1H NMR (300 MHz,CD2Cl2): d=1.45–2.01 (brm, 16H; C=
CH2CH2), 2.45–2.78 (brm, 8H; C=CH2), 2.98–3.17 (m, 8H; C=CH2), 7.20
(s, 4H; Hc), 7.27 (brs, 8H; H5 Py), 7.33–7.54 (m, 28H; Hph and Ha), 7.59
(d, 3J
(H,H)=8.2 Hz, 8H; Hb), 7.68 (d, 3J
ACHUTGTNRNEGUN ACHTUNTGNER(NUGN H,H)=7.2 Hz, 8 H; H3 Py),
Synthesis of supramolecular assembly (14a): Following the general proce-
dure, the reaction of 2a (0.200 g, 0.16 mmol) with 3 (1 equiv, 0.037 g,
0.16 mmol) afforded 14a as an air-stable red solid (0.138 g, 0.05 mmol,
62% yield). 1H NMR (300 MHz, CD2Cl2): d=1.07–1.23 (m, 4H; C=
CH2CH2), 1.28–1.45 (m, 4H; C=CH2CH2), 1.52–1.69 (m, 4H; C=
CH2CH2), 1.71–1.86 (m, 4H; C=CH2CH2), 2.41–2.61 (m, 4H; C=CH2),
2.85–3.00 (m, 4H; C=CH2), 3.04–3.20 (m, 4H; C=CH2), 3.32–3.50 (m,
4H; C=CH2), 6.30–6.46 (m, 4H; Hanthracene), 6.47–6.56 (m, 4H; Hanthracene),
7.96 (dd, 3J
ACTHNUGTRNE(NGU H,H)=7.2, 7.5 Hz, 8H; 8H; H4 Py), 8.45 ppm (brs, 8H; H6
Py); 31P{1H} NMR (121.5 MHz, CD2Cl2): d=ꢀ144.9 (sept, 1J
ACHTUNGTRENNUNG(P,F)=
711 Hz, PF6), 8.7 ppm (brm, n1/2 =128.0 Hz, Pphosphole); elemental analysis
calcd (%) for C129H106Cl2Cu4F24N12P8 (16aꢄCH2Cl2, 2848.27 gmolꢀ1): C
54.30, H 3.74, N 5.89;. found: C 54.63, H 3.55, N 5.65.
Synthesis of supramolecular assembly (16b): Following the general pro-
cedure, the reaction of 2b (0.200 g, 0.16 mmol) with connector 5 (1 equiv,
0.037 g, 0.16 mmol) afforded 16b as an air-stable orange-yellow solid
(0.141 g, 0.05 mmol, 63% yield). 1H NMR (500 MHz, CD2Cl2/CD3CN):
d=1.61–1.68 (m, 4H; C=CH2CH2), 1.83–1.90 (m, 4H; C=CH2CH2), 2.17–
6.77–6.96 (m, 4H; Hanthracene), 7.23 (t, 3J
7.28–7.45 (m, 20H; H5’ Py, Hanthracene, o-Ph and p-Ph), 7.60 (d, J
7.5 Hz, 4H; H3’ Py), 7.68 (dd, 3J(H5,H6)=5.2 Hz, 3J
(H5,H4)=7.1 Hz, 4H;
H5 Py), 7.95 (dd, 3J(H4’,H5’)=7.4 Hz, 3J
(H4’,H3’)=7.5 Hz, 4H; H4’ Py),
8.32 (d, 3J(H3,H4)=8.0 Hz, 4H; H3 Py), 8.39 (d, 4H; 3J
(H6’,H5’)=4.9 Hz,
H6’ Py), 8.46 (dd, 3J(H4,H5)=7.1 Hz, 3J
(H4,H3)=8.0 Hz, 4H; H4 Py),
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
2.36 (m, 4H; C=CCH2), 2.88 (dt, 3J
2H; Hd), 3.07–3.21 (m, 4H; C=CCH2), 3.72 (dt, 3J
12.60 Hz, 2H; Hd), 6.97 (d, 3J
(H,H)=7.61 Hz, 8H; Hph), 7.15 (t,
3J(H,H)=7.30, 7.61 Hz, 8H; Hph), 7.20 (t, 3J
(H,H)=7.46, 7.46 Hz, 8H;
ph), 7.26 (t, 3J
(H,H)=7.30, 7.30 Hz, 4H; Hph), 7.3–7.41 (brm, 12H; 4H5
Py, 8Hph), 7.47 (dt, 3J
(H,H)=6.05, 5.79 Hz, 8H; HPh), 7.54 (s, 4H; Ha),
7.62 (t, 3J
(H,H)=7.26, 7.26 Hz, 4H; HPh), 7.83–7.88 (m, 20H; H3 Py,
Ph), 7.96 (t, J
(H,H)=11.09 Hz, 2J
ACHUTGTNRENNUG CAHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
8.70 ppm (d, 3J(H6,H5)=5.2 Hz, 4H; H6 Py); 31P{1H} NMR (CD2Cl2,
A
ACHTUNGTRENNUNG
121.5 MHz): d=ꢀ144.3 (sept,1J
AHCTUNGRTEGNUN(N P,F)=710 Hz, PF6), 3.2 ppm (brs,
H
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
Pphosphole); elemental analysis calcd (%) for C129H103Cu4F24N12P8
(2779.21 gmolꢀ1): C 55.75, H 3.74, N, 6.05; found: C 55.81, H 3.69, N
6.00.
AHCTUNGTRENNUNG
3
3
H
ACHUTGTNRENNUG(H,H)=7.45, 7.45 Hz, 4H; H4 Py), 8.64 ppm (d, JACHTUNGTRENNUNG(H,H)=
4.80 Hz, 4H; H6 Py); 13C{1H} NMR (125.77 MHz, CD2Cl2/CD3CN,): d=
21.6 (s, C=CCH2CH2), 24.3 (brs, Cd), 27.5 (s, C=CCH2), 123.6 (s, C5 Py),
124.4 (s, C3 Py), 127.6 (brs, CPh), 128.8 (brs, CPh), 129.6 (brs, CPh), 130.4
(s, C6), 132.7 (brs, CPh), 133.5 (brs, CPh), 139.0 (s, C4 Py), 150.2 ppm (s, C6
Py); C2 Py, Ca, Cb, and ipso-Ph were not observed; 31P{1H} NMR
Synthesis of supramolecular assembly (14b): Following the general pro-
cedure, the reaction of 2b (0.200 g, 0.16 mmol) with 3 (1 equiv, 0.037 g,
0.16 mmol) afforded 14b as an air-stable red solid (0.161 g, 0.056 mmol,
70% yield). 31P{1H} NMR (CD2Cl2, 121.5 MHz): d=ꢀ144.1 (sept,
1J
(P,F)=711 Hz, PF6), ꢀ1.2 (brs, Pdppm), 14.5 ppm (brs, Pphosphole); elemen-
(121.5 MHz, CD2Cl2/CD3CN): d=ꢀ144.4 (sept, 1J
ACHTUNGTREN(NUNG P,F)=711 Hz, PF6),
tal analysis calcd (%) for C131H104Cl2Cu4F24N8P10 (14bꢄCH2Cl2;
2876.19 gmolꢀ1): C 54.61, H 3.64, N 3.89; found: C 54.83; H 3.59; N 4.02.
ꢀ3.4 (d, 2J
(P,P)=84 Hz, 2P, Pdppm), 12.8 (t, 2J
CAHTUTGNRNEUNG ACHTUNGTRENN(NGU P,P)=84, 84 Hz, Pphosphole);
Chem. Eur. J. 2010, 16, 7143 – 7163
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
7157

R. Rꢂau, C. Lescop et al.
elemental analysis calcd (%) for C130H106Cu4F24N8P10 (2796.28 gmolꢀ1): C
55.76, H 3.82, N 4.00; found: C 55.45, H 3.65, N 5.85.
(m, 8H; C=CH2), 7.25 (d, 3J
20H; HPh), 7.58 (s, 8H; Hc), 7.67–7.88 (brm, 24H; Ha, Hb and H3 Py),
ACHTUNGTRNE(NGNU H,H)=6.8 Hz, 8H; H5 Py), 7.32–7.53 (brm,
7.93 (dd, 3J
ACHTUNTRGNEG(UN H,H)=7.2, 7.4 Hz, 8H; H4 Py), 8.44 ppm (brs, 8H; H6 Py);
Synthesis of supramolecular assembly (17a): Following the general proce-
dure, the reaction of 2a (0.400 g, 0.32 mmol) with 6 (1 equiv, 0.106 g,
0.32 mmol) afforded after crystallization 17a as an air-stable red solid
(0.313 g, 0.10 mmol, 63% yield). 1H NMR (300 MHz, CD2Cl2): d=1.57–
1.76 (m, 8H; C=CH2CH2), 1.90–2.05 (m, 8H; C=CH2CH2), 2.38–2.55 (m,
8H; C=CH2), 3.10–3.25 (m, 8H; C=CH2), 6.70–6.81 (m, 8H; HPh),7.03–
31P{1H} NMR (CD2Cl2, 121.5 MHz): 7.9 (brs, Pphosphole); elemental analysis
calcd (%) for C146H112B4Cl4Cu4F16N12P8 (21aꢄ2CH2Cl2; 2896.41 gmolꢀ1):
C 60.43, H 3.89, N 5.79; found: C 60.11, H 3.62, N 5.47.
Synthesis of supramolecular assembly (22a): Following the general proce-
dure, the reaction of 2a (0.400 g, 0.32 mmol) with 11 (1 equiv, 0.106 g,
0.32 mmol) afforded after crystallization 22a as an air-stable red solid
(0.298 g, 0.10 mmol, 62% yield). 1H NMR (300 MHz,CD2Cl2): d=1.22–
1.95 (brm, 16H; C=CH2CH2), 2.08–2.43 (brm, 8H; C=CH2), 2.58–3.22
7.08 (m, 8H; HPh), 6.90 (d, 3J
3J(H,H)=16.3 Hz, 4H; Hc), 7.32 (t, 3J
(d,3J(H,H)=6.5 Hz, 8H; H5 Py), 7.53 (d, 3J
ACHTUNGTRENNUNG ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
7.62 (s, 8H; He), 7.66 (d, 3J
G
ACHTUNGTRENNUNG
(m, 8H; C=CH2CH2), 6.73 (d, 3J
ACHTNUTRGNE(UNG H,H)=16 Hz, 4H; Hc), 7.06–7.14 (m,
3
8.3 Hz, 8H; Ha) 7.80 (t, J
(H,H)=6.5, 8.1 Hz, 8H; H4 Py), 8.35 ppm (brs,
4H; Hf), 7.22–7.48 (m, 36H; HPh, H5 Py and He,d), 7.48–7.62 (m, 24H; H3
and Ha,b), 7.83 (brs, 8H; H4 Py), 8.36 ppm (brs, 8H; H6 Py); 31P{1H}
8H; H6 Py). 31P{1H} NMR (CD2Cl2, 121.5 MHz): d=ꢀ141.0 (sept,
1J
ACHTUNGTRENNUNG(P,F)=709 Hz, PF6), 8.7 ppm (brs, Pphosphole); elemental analysis calcd
NMR (CD2Cl2, 121.5 MHz): d=ꢀ143.4 (sept, 1J
ACHTUNGTREN(NUNG P, F)=703 Hz, PF6),
(%) for C145H118Cl2Cu4F24N12P8 (17aꢄCH2Cl2 3052.37 gmolꢀ1): C 56.96,
7.80 ppm (brs); elemental analysis calcd (%) for C145H118Cl2Cu4F24N12P8
(22aꢄCH2Cl2; 3052.37 gmolꢀ1): C 56.96, H 3.89, N 5.50; found: C 57.15,
H 3.74, N 5.73.
H 3.89, N 5.50;. found: C 57.23, H 3.67, N 5.83.
Synthesis of supramolecular assembly (17b): Following the general pro-
cedure, the reaction of 2b (0.400 g, 0.42 mmol) with 6 (1 equiv, 0.16 g,
0.42 mmol) afforded 17b as an air-stable yellow solid (0.798 g, 65%
yield). 1H NMR(300 MHz, CD2Cl2): d=1.57–1.76 (m, 4H; C=CH2CH2),
1.90–2.05 (m, 4H; C=CH2CH2), 2.38–2.55 (m, 4H; C=CH2), 2.87–3.00 (m,
2H; Hd), 3.10–3.25 (m, 4H; C=CH2), 3.35–3.55 (m, 2H; Hd), 6.70 (m,
Synthesis of supramolecular assembly (23a): Following the general proce-
dure, the reaction of 2a (0.400 g, 0.36 mmol) with 12 (1 equiv, 0.106 g,
0.32 mmol) afforded after crystallization 23a as an air-stable red solid
(0.284 g, 0.10 mmol, 56% yield). 1H NMR (300 MHz, CD2Cl2): d=1.57–
1.76 (m, 8H; C=CH2CH2), 1.90–2.05 (m, 8H; C=CH2CH2), 2.38–2.55 (m,
8H; m-Phdppm), 7.03 (m, 8H; m-Phdppm), 6.90 (d, 3J
Hd), 7.14 (d, 3J(H,H)=16.3 Hz, 4H; Hc), 7.32 (t, 3J
4H; m-Ph), 7.37 (d, 3J
(H,H)=6.5 Hz, 4H; H5 Py),7.39–7.51 (m, 30H; o-
and p-Phdppm, o- and p-Ph), 7.53 (d, J
8H; He), 7.66 (d, 3J(H,H)=8.3 Hz, 8H; Hb), 7.71 (d, 3J
8H; Ha), 7.80 (dd, 3J
ACHTUNGTRENNUNG
3
8H; C=CH2), 3.10–3.25 (m, 8H; C=CH2), 7.14 (d, J
N
3
A
ACHTUNGTRENNUNG
Hc), 7.20 (d, JACTHNURTGNEUNG(H,H)=16.5 Hz, 4H; H7), 7.32–7.49 (m, 34H; Hph, Ha, He,
3
3
ACHTUNGTRENNUNG
Hf), 7.27 (d, J
H3 Py),7.65 (d, 3J
3J(H,H)=6.9, 8.1 Hz, 8H; H4 Py), 8.48 ppm (brs, 8H; H6 Py); 31P{1H}
G
ACHTUNGTREN(NGNU H,H)=8.1 Hz, 8H;
3
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG(H,H)=6.5, 8.1 Hz, 4H; H4 Py), 8.35 ppm (brs, 4H;
NMR (CD2Cl2, 121.5 MHz): d=7.70 (brs, Pphosphole); elemental analysis
calcd (%) for C144H116B4Cu4F16N12P4 (2739.84 gmolꢀ1): C 63.13, H 4.27, N
6.13; found: C 63.01, H 4.22, N 5.91.
H6 Py); 31P{1H} NMR (CD2Cl2, 121.5 MHz): d=ꢀ144.3 (sept, 1J
ACHTUNGTRENNUNG
709.5 Hz, PF6), 0.40 (d, 2J(P,P)=72.9 Hz, Pdppm), 16.50 ppm (t, 2J
ACTHNUGTRENNUGN ACHTUNGTRENNNUG
72.9 Hz, Pphosphole); elemental analysis calcd (%) for C146H118Cu4F24N8P10
(3004.44): C 58.37, H 3.96, N, 3.73; found: C 58.61, H, 3.79, N 3.80.
Synthesis of supramolecular assembly (24a): Following the general proce-
dure, the reaction of 2a (0.400 g, 0.32 mmol) with 13 (1 equiv, 0.107 g,
0.32 mmol) afforded after crystallization 24a as an air-stable red solid
(0.304 g, 0.12 mmol, 75% yield). 1H NMR (200 MHz, CD2Cl2): d=1.75–
1.90 (m, 8H; C=CH2CH2), 2.32–2.62 (m, 4H; C=CH2), 2.89–3.00 (m, 8H;
C=CH2), 7.00–7.30 (m, 32H; H5 Py, m, p-Ph, Hc, Hd, He), 7.31–7.40 (m,
8H; H3 Py), 7.45–7.59 (m, 16H; Ha and Hb), 7.55–7.69 (m, 8H; o-Ph),
7.82–7.98 (m, 10H; H4 Py and Hf), 8.43 ppm (brs, 8H; H6 Py); 31P{1H}
Synthesis of supramolecular assembly (18a): Following the general proce-
dure, the reaction of 2a (51.2 g, 0.046 mmol) with 7 (1 equiv, 20 mg,
0.046 mmol) dissolved in CH2Cl2 (100 mL) afforded after crystallization
18a as an air-stable red solid (13 g, 0.010 mmol, 20% yield). 31P{1H}
NMR (CD2Cl2, 121.5 MHz): d=7.5 ppm (brs); elemental analysis calcd
(%) for C162H132B4Cl4Cu4F16N12P4 (18aꢄ2CH2Cl2; 3108.57 gmolꢀ1):
C
NMR (CD2Cl2, 121.5 MHz): d=ꢀ143.4 (sept, 1J
ACHTUNGTREN(NUNG P, F)=703 Hz, PF6),
62.48, H 4.27, N 5.40; found: C 62.64, H 4.56, N 5.17.
Synthesis of supramolecular assembly (19a): Following the general proce-
dure, the reaction of 2a (0.168 g, 0.136 mmol) with 8 (1 equiv, 0.028 g,
0.137 mmol) afforded after crystallization 19a as an air-stable orange
solid (0.12 g, 0.044 mmol, 65% yield). 1H NMR (500 MHz, CD2Cl2): d=
1.83–1.95 (brs, 16H; C=CH2CH2), 3.03–3.17 (brs, 16H; C=CH2), 7.35–
7.42 (brm, 28H; H5 Py, o,m,p-Ph), 7.47 (s, 8H; Hb), 7.64 (s, 8H; Ha),
7.60–7.68 (brs, 8H; H4 Py), 7.95–8.06 (brs, 8H; H3 Py), 8.38–8.55 ppm
7.49 ppm (brs); elemental analysis calcd (%) for C143H116Cl2Cu4F24N14P8
(24aꢄCH2Cl2; 3054.36 gmolꢀ1): C 56.14, H 3.82, N 6.41; found: C 56.31,
H 3.77, N 6.47.
X-ray crystallographic study: Single crystals suitable for X-ray crystal
analysis were obtained by slow diffusion of vapors of pentane into a di-
chloromethane solution of p-conjugated connectors 5 and 6 and of supra-
molecular assemblies 14a,b, 15a,b, 16a,b1,b2, 17a, 18a, 19a, 20a, 21a,
22a, 23a and 24a at room temperature. Single-crystal data collection was
performed at 120 K with a Nonius KappaCCD diffractometer or at 100 K
with an APEX II Bruker-AXS (Centre de Diffractomꢂtrie, Universitꢂ de
Rennes 1, France) with MoKa radiation (l=0.71073 ꢁ). Reflections were
indexed, Lorentz-polarization corrected and integrated by the DENZO
program of the KappaCCD software package. The data merging process
was performed using the SCALEPACK program.[50] Structure determina-
tions were performed by direct methods with the solving program
SIR97,[51] that revealed all the non-hydrogen atoms. The SHELXL pro-
gram[52] was used to refine the structures by full-matrix least-squares
based on F2. All non-hydrogen atoms were refined with anisotropic dis-
placement parameters. Hydrogen atoms were included in idealized posi-
tions and refined with isotropic displacement parameters. In the crystal
lattices of the coordination complexes studied, dichloromethane solvent
molecules were found in addition to the cationic coordination complexes
and to their counterions (hexafluorophosphate for 14a,b, 15a,b, 16a,b1,
17a, 19a, 20a, 22a, 24a and tetrafluoroborate for 21a and 23a). These
solvent molecules in most cases have a strong tendency to leave the bulk
crystal through evaporation once the crystals are removed from their
mother solution, a process that induces a rapid degradation of the single-
crystal integrity of the crystals investigated. In order to slow down this
(brs, 8H; H6 Py). 31P{1H} NMR (CDCl3, 81 MHz): d=ꢀ139.4 (sept, 1J
ACHTUNGERTN(NUNG P,
F)=700 Hz, PF6), 8.9 (brs, n1/2 =150 Hz, Hphosphole); elemental analysis
calcd (%) for C124H100Cu4F24N12P8 (2712.29 gmolꢀ1): C 54.83, H 3.71, N
6.19; found: C 54.98, H 3.66, N 6.11.
Synthesis of supramolecular assembly (20a): Following the general proce-
dure, the reaction of 2a (0.400 g, 0.32 mmol) with 9 (1 equiv, 0.114 g,
0.32 mmol) afforded after crystallization 20a as an air-stable red solid
(0.328 g, 0.11 mmol, 69% yield). 1H NMR (300 MHz, CDCl3): d=1.62
(brs, 8H; C=CH2CH2), 1.97–1.80 (m, 8H; C=CH2CH2), 2.71–2.4 (m, 8H;
C=CH2), 3.02–2.98 (m, 8H; C=CH2), 7.3 (d, J
7.42 (t, 3J
(H,H)=7.4 Hz, 20H; HPh), 7.62 (d, J
Py), 7.66 (dd, JACHTUNGTRENNUNG(H,H)=18.3, 8.4 Hz, 32H; HAr), 7.95 (t, JACHTUNGRTEN(NUNG H,H)=7.9 Hz,
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
3
3
8H; H4 Py), 8.51 ppm (brs, 8H; H6 Py). 31P{1H} NMR (CD2Cl2,
121.5 MHz): d=ꢀ142.4 (sept, 1J
ACHTUNGRTEN(NUNG P, F)=702 Hz, PF6), 6.8 ppm (br,
Pphosphole); elemental analysis calcd (%) for C148H116Cu4F24N12P8
(3016.41 gmolꢀ1): C 58.85, H 3.87, N 5.56; found: C 58.65, H 3.74, N 5.21.
Synthesis of supramolecular assembly (21a): Following the general proce-
dure, the reaction of 2a (0.203 g, 0.18 mmol) with 10 (1 equiv, 0.060 g,
0.18 mmol) afforded after crystallization 21a as an air-stable red solid
(0.164 g, 0.06 mmol, 67% yield). 1H NMR (300 MHz, CD2Cl2): d=1.41–
2.01 (brm, 16H; C=CH2CH2), 2.45–2.73 (brm, 8H; C=CH2), 2.92–3.18
7158
www.chemeurj.org
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 7143 – 7163

Supramolecular Chemistry
FULL PAPER
process, single crystals of all these derivatives were always coated in
paraACHTUNGTRENNUNGtone oil once removed from the mother solution, mounted at low
parameters, and derivative 24a are isostructural). The crystallographic
data for the derivatives 19a, 20a, 22a, 23a and 24a after this squeeze
treatment are given in Tables 5 and 6. Table S1 (see Supporting Informa-
tion) gives the crystallographic data for the derivatives 19a, 20a, 22a,
23a and 24a before squeeze treatment. Finally, in the case of the supra-
molecular assemblies 16b2 and 18a, disordered CH2Cl2 molecules and
disordered counterions were highly delocalized and it was not possible to
localize them. We used a squeeze treatment in order to remove the scat-
tering contribution of these molecules (CH2Cl2 molecules and counter-
ions) which could not be satisfactory modeled. Table 5 gives the crystallo-
graphic data for the derivatives 16b2 and 18a after this squeeze treat-
ment. Table S1 (see Supporting Information) gives the crystallographic
data for the derivatives 16b2 and 18a before such squeeze treatment. In
addition, in the case of the derivative 16b2 one part of the styryl moiety
of one of the ditopic connector 5 is disordered into two positions that
were refined with relative occupancy. As a consequence and due to the
poor quality of the X-ray data collection for the crystals of 16b2 due to
rapid desolvatation of the included solvent molecules, some of the atoms
involved in this disorder modeling had to be refined with isotropic dis-
placement parameters. Finally, in the case of derivative 18a, the central
double bond of the ditopic connector 18a was disordered into two statis-
tically equal positions. The modeling of the resulting disorder was not
possible for the atoms of the neighboring phenyl rings. As a consequence,
some of these atoms have rather high anisotropic displacement parame-
ters. Atomic scattering factors for all atoms were taken from Internation-
al Tables for X-ray Crystallography.[53] CCDC-293234 (15a), 293235
(15b), 293236 (14a,), 293237 (14b), 293238 (16a), 293239 (16b1), 293240
(17a), 293241 (5), 293242 (6), 755226 (16b2), 755227 (18a), 755228 (19a),
755229 (20a), 755230 (21a), 755231 (22a), 755232 (23a), and 755234
(24a) contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge Crystal-
lographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
temperature (100 K) as quickly as possible on the diffractometer gionom-
eter and X-ray data collection were performed at low temperature
(100 K). In most cases, X-ray crystal structure resolution revealed these
solvent molecules to be highly disordered. In the case of the supramolec-
ular assemblies 14a,b, 15a,b, 16a,b1, 17a and 21a, modeling of the disor-
der of these solvent molecules was possible leading to rather high aniso-
tropic displacement parameters for some of their atoms. As a conse-
quence, final agreement (R) factors were determined with modest values
in some cases. Nevertheless, anisotropic displacement parameters associ-
ated to the atoms of the cationic coordination complexes were always
satisfactory. This allowed a primarily assignment of these modest R fac-
tors to an inadequate modeling of the disordered species exterior to
these supramolecular assemblies and gave confidence to the treatment of
the structural resolution of these derivatives. In addition, in the case of
derivative 17a, one part of the styryl moiety of the ditopic connector 17a
was disordered into two statistically nearly equal positions. The modeling
of this disorder was not possible for the atoms of the neighboring phenyl
rings. As a consequence, some of these atoms have rather high anisotrop-
ic displacement parameters. The crystallographic data for the derivatives
14a,b, 15a,b, 16a,b1, 17a and 21a are given in Tables 4–6 In the case of
the supramolecular assemblies 19a, 20a, 22a, 23a and 24a, disordered
CH2Cl2 molecules occupy an important volume of the crystal cell and
were found highly disorder. A modeling of these disorders was not possi-
ble and we used a “squeeze” treatment in order to remove the scattering
contribution of these molecules, which could not be satisfactory modeled.
In these cases, anisotropic displacement parameters associated with the
atoms of the cationic coordination complexes were always satisfactory
except in the case of the derivative 24a, for which two carbon atoms
were refined with isotropic displacement parameters (derivatives 23a, for
which all atoms were refined with satisfactory anisotropic displacement
Table 4. Crystal data and structure refinement for p-conjugated connectors 5 and 6 and of supramolecular assemblies 14a,b, 15a,b.
5
2.56
14a
[PF6]4·12CH2Cl2 14b
N
15aACTHGNUTRENNU[G PF6]4·11CH2Cl2 15bACTHUGNTREN[NUNG PF6]4·8CH2Cl2
formula
C8H5N
C60H40N5
C128H33Cu4F24N12P8·
12CH2Cl2
3771.14
C114H82Cu4F24N8P10·
8CH2Cl2
3263.14
11.877(1)
16.286(1)
18.499(1)
99.877(2)
103.361(2)
93.677(2)
3410(1)
6CH2Cl2
3127.70
11.563(5)
13.188(5)
22.355(5)
84.912(5)
80.661(5)
76.286(5)
3263(2)
1
11CH2Cl2
3491.95
14.570(5)
15.755(5)
16.378(5)
81.781(5)
72.909(5)
86.587(5)
3556(2)
1
Mr
115.13
830.97
a [ꢀ]
b [ꢀ]
c [ꢀ]
a [8]
4.7529(3)
10.5673(6)
11.9098(6)
90
97.9080(10)
90
592.48(6)
4
0.077
9.925(5)
12.407(5)
17.888(5)
98.691(5)
100.221(5)
91.726(5)
2139.2(15)
2
15.496(1)
15.617(2)
16.510(1)
97.191(2)
99.695(1)
98.600(2)
3847.5(6)
1
b [8]
g [8]
V [ꢁ3]
Z
1
1calcd [Mgmꢀ3
]
1.290
1.628
1.591
1.631
1.589
crystal system
space group
T [K]
monoclinic
P21/c
120(2)
triclinic
P1
120(2)
triclinic
P1
100(2)
triclinic
P1
100(2)
triclinic
P1
120(2)
triclinic
P1
100(2)
¯
¯
¯
¯
¯
crystal size [mm]
0.4ꢄ0.15ꢄ0.15 0.3ꢄ0.3ꢄ0.1
0.2ꢄ0.2ꢄ0.1
1.129
0.4ꢄ0.4ꢄ0.3
1.019
0.3ꢄ0.2ꢄ0.1
1.178
0.1ꢄ0.1ꢄ0.1
1.130
m (MoKa) [cmꢀ1
]
0.077
0.076
F
(000)
240
870
1896
1580
1750
1640
q range [8]
index ranges
3.45–27.46
ꢀ6ꢂhꢂ6
ꢀ11ꢂkꢂ13
ꢀ10ꢂlꢂ15
4517
1.66–27.56
ꢀ12ꢂhꢂ12
ꢀ16ꢂkꢂ16
ꢀ23ꢂlꢂ23
31829
1.27–27.55
ꢀ20ꢂhꢂ20
ꢀ20ꢂkꢂ20
ꢀ21ꢂlꢂ21
69250
2.77–27.49
ꢀ15ꢂhꢂ15
ꢀ17ꢂkꢂ17
ꢀ29ꢂlꢂ29
28203
3.32–27.51
ꢀ18ꢂhꢂ18
ꢀ20ꢂkꢂ20
ꢀ21ꢂlꢂ21
29496
5.23–27.57
ꢀ15ꢂhꢂ15
ꢀ21ꢂkꢂ19
ꢀ23ꢂlꢂ24
28183
reflns collected
independent reflns
1347
31829
17704
14878
16116
15415
reflections [I>2s(I)]
data/restraints/parameters
goodness-of-fit on F2
final R indices [I>2s(I)]
1206
1347/0/82
1.077
R1=0.0366
wR2=0.1055
R1=0.0404
wR2=0.1086
0.319/ꢀ0.196
7681
9791/0/587
1.034
14080
17704/0/958
1.054
12262
14878/0/875
1.020
R1=0.0617
wR2=0.1588
R1=0.0752
wR2=0.1706
2.874/ꢀ2.005
13381
16116/0/851
1.031
R1=0.0657
wR2=0.1858
R1=0.0792
wR2=0.2024
1.551/ꢀ1.105
9119
15415/0/856
1.040
R1=0.0809
wR2=0.2101
R1=0.1435
wR2=0.2471
0.889/ꢀ0.765
R1=0.0452
R1=0.0781
wR2=0.1209 wR2=0.2138
R1=0.0611 R1=0.0990
wR2=0.1330 wR2=0.2385
0.720/ꢀ0.363 3.180/ꢀ2.225
R indices (all data)
largest diff peak/hole [eꢁꢀ3
]
Chem. Eur. J. 2010, 16, 7143 – 7163
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
7159

R. Rꢂau, C. Lescop et al.
Table 5. Crystal data and structure refinement for supramolecular assemblies 16a,b1,b2, 17a, 18a, 19a.
16a[PF6]4·6CH2Cl2 16b 17a[PF6]4·14CH2Cl2 18a
1[PF6]4·5CH2Cl2 16b2
C128H104Cu4F24N12P8· C130H102Cu4F24N8P10· C130H106Cu4N8P6 C141H100Cu4F24N12P8· C106H128Cu4N12P4 C124H100Cu4F24N12P8
A
E
N
19aACHTGNURETNNU[G PF6]4
formula
6CH2Cl2
3277.71
12.9509(5)
16.0253(8)
17.0867(9)
84.578(2)
86.377(2)
77.343(2)
3441.3(3)
1
5CH2Cl2
3220.69
14CH2Cl2
4056.47
13.525(11)
19.33(2)
20.169(16)
104.45(3)
107.66(2)
103.88(3)
4571(7)
1
Mr
2220.21
11.80(3)
23.32(6)
27.10(8)
105.88(12)
99.86(8)
97.90(8)
6932(32)
2
2596.78
13.325(1)
16.907(1)
19.953(2)
70.267(4)
87.088(4)
79.459(5)
4131.4(7)
1
2716.08
a [ꢀ]
b [ꢀ]
c [ꢀ]
a [8]
21.005(5)
24.342(5)
28.028(5)
90.000(5)
106.742(5)
90.000(5)
13723(5)
4
29.377(1)
14.884(1)
32.264(1)
90
96.641(1)
90
14013(1)
4
1.287
b [8]
g [8]
V [ꢁ3]
Z
1calcd [Mgmꢀ3
]
1.582
1.559
1.064
1.474
1.044
crystal system
space group
T [K]
triclinic
P1
100(2)
monoclinic
P21/a
100(2)
triclinic
P1
95(2)
triclinic
P1
120(2)
triclinic
P1
100(2)
monoclinic
C2/c
100(2)
¯
¯
¯
¯
crystal size [mm]
0.2ꢄ0.1ꢄ0.05
1.023
0.15ꢄ0.10ꢄ0.05
1.009
0.1ꢄ0.06ꢄ0.04 0.3ꢄ0.15ꢄ0.1
0.4ꢄ0.15ꢄ0.05
0.593
0.1ꢄ0.07ꢄ0.02
0.770
m (MoKa) [cmꢀ1
]
0.718
0.991
F
(000)
1660
6520
2296
2045
1348
5520
q range [8]
index ranges
2.40–27.53
ꢀ16ꢂhꢂ16
ꢀ20ꢂkꢂ20
ꢀ22ꢂlꢂ22
67250
0.76–27.64
ꢀ27ꢂhꢂ27
ꢀ28ꢂkꢂ31
ꢀ36ꢂlꢂ35
174440
2.08–27.64
ꢀ15ꢂhꢂ15
ꢀ30ꢂkꢂ30
ꢀ34ꢂlꢂ34
55915
2.24–27.6
ꢀ17ꢂhꢂ17
ꢀ24ꢂkꢂ24
ꢀ26ꢂlꢂ25
73592
1.30–26.33
ꢀ16ꢂhꢂ15
ꢀ21ꢂkꢂ15
ꢀ24ꢂlꢂ21
19797
2.74–26.00
ꢀ36ꢂhꢂ35
ꢀ18ꢂkꢂ18
ꢀ39ꢂlꢂ39
25131
reflns collected
independent reflns
15751
31738
31185
19939
15374
13544
reflections [I>2s(I)]
data/restraints/parameters
goodness-of-fit on F2
final R indices [I>2s(I)]
10128
15751/0/874
1.017
R1=0.0578
wR2=0.1432
R1=0.1067
wR2=0.16666
1.189/ꢀ1.061
13094
31738/0/1765
1.028
R1=0.0745
wR2=0.1806
R1=0.2162
wR2=0.2446
1.011/ꢀ0.855
9284
31185/0/1295
0.767
R1=0.0932
wR2=0.1909
R1=0.2251
wR2=0.2286
1.526/ꢀ0.701
9172
19939/0/1148
1.053
R1=0.0927
wR2=0.2487
R1=0.2050
wR2=0.3059
1.016/ꢀ1.558
7000
15374/0/820
0.851
R1=0.0750
wR2=0.1781
R1=0.1397
wR2=0.2011
0.985/ꢀ0.639
5732
13554/0/775
0.985
R1=0.1049
wR2=0.2642
R1=0.2040
wR2=0.3075
1.250/ꢀ0.662
R indices (all data)
largest diff peak/hole [eꢁꢀ3
]
Table 6. Crystal data and structure refinement for supramolecular assemblies 20a, 21a, 22a, 23a and 24a.
20a[PF6]4 21a[BF4]4·6CH2Cl2 222a[PF6]4
G
E
E
23a
G
24aACHTGNURETNNU[G PF6]4
formula
C148H116Cu4F24N12P8
C144H108Cu4F16N12P4B4·
6CH2Cl2
3241.266
13.893(2)
15.642(3)
20.412(3)
111.880(8)
107.299(9)
102.844(9)
3641.7(11)
1
C288H232Cu8F48N24P16
C144H116B4Cu4F16N12P4
C142H114Cu4F24N14P8
Mr
3020.45
6005.05
16.886(2)
21.426(2)
22.094(2)
90.696(5)
98.891(5)
102.940(5)
7688(2)
1
2739.77
2974.39
a [ꢀ]
b [ꢀ]
c [ꢀ]
a [8]
20.456(2)
35.311(3)
24.437(2)
90
99.287(5)
90
17420(1)
4
1.152
14.990(3)
31.892(5)
40.379(6)
90
90
90
19304(5)
4
0.943
14.825(2)
31.840(4)
39.873(6)
90
90
90
18821(4)
4
1.050
b [8]
g [8]
V [ꢁ3]
Z
1calcd [Mgmꢀ3
]
1.478
1.297
crystal system
space group
T [K]
monoclinic
P21/n
100(2)
triclinic
P1
100(2)
triclinic
P1
100(2)
orthorhombic
Pbcn
100(2)
orthorhombic
Pbcn
100(2)
¯
¯
crystal size [mm]
0.3ꢄ0.1ꢄ0.03
0.626
0.18ꢄ0.12ꢄ0.05
0.917
0.2ꢄ0.2ꢄ0.1
0.710
0.2ꢄ0.1ꢄ0.03
0.522
0.12ꢄ0.10ꢄ0.03
0.578
m (MoKa) [cmꢀ1
]
F
(000)
6160
1648
3061
5616
6064
q range [8]
index ranges
1.02–27.73
ꢀ26ꢂhꢂ23
ꢀ46ꢂkꢂ46
ꢀ19ꢂlꢂ31
158872
1.18–26.42
ꢀ17ꢂhꢂ17
ꢀ19ꢂkꢂ19
ꢀ25ꢂlꢂ25
35083
1.25–26.72
ꢀ21ꢂhꢂ21
ꢀ26ꢂkꢂ26
ꢀ27ꢂlꢂ27
99148
2.77–27.49
ꢀ18ꢂhꢂ17
ꢀ19ꢂkꢂ39
ꢀ49ꢂlꢂ49
81149
1.02–26.17
ꢀ18ꢂhꢂ12
ꢀ39ꢂkꢂ22
ꢀ34ꢂlꢂ49
93107
reflns collected
independent reflns
40558
14849
31674
19439
18786
reflections [I>2s(I)]
data/restraints/parameters
goodness-of-fit on F2
final R indices [I>2s(I)]
12108
40558/0/1765
0.919
R1=0.0851
wR2=0.2014
R1=0.2215
wR2=0.2324
0.792/ꢀ0.665
11387
14849/0/911
1.076
R1=0.0638
wR2=0.1776
R1=0.0879
wR2=0.2058
1.425/ꢀ1.070
16748
31674/0/1799
1.044
R1=0.0972
wR2=0.2751
R1=0.1495
wR2=0.3002
1.916/ꢀ0.908
7301
19439/0/829
0.828
R1=0.0785
wR2=0.1669
R1=0.1831
wR2=0.1923
1.042/ꢀ0.547
5264
18786/6/807
0.792
R1=0.0838
wR2=0.2054
R1=0.2456
wR2=0.2455
0.997/ꢀ0.605
R indices (all data)
largest diff peak/hole [eꢁꢀ3
]
7160
www.chemeurj.org
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 7143 – 7163

Supramolecular Chemistry
FULL PAPER
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Acknowledgements
We thank the Ministꢅre de la Recherche et de l’Enseignement Supꢂrieur,
the Institut Universitaire de France, the CNRS, and the ANR (Projet
Phoshelix-137104). Thanks are due to Dr. T. Roisnel (Centre de Diffrac-
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