Dissymmetrical U-shaped π-stacked supramolecular assemblies by using a dinuclear CuI clip with organophosphorus ligands and monotopic fully π-conjugated ligands

Article abstract of DOI:10.1002/chem.201403758

Reactions between the U-shaped binuclear Cu^I complex A that bears short metal-metal distances and the cyano-capped monotopic π-conjugated ligands 1-5 that carry gradually bulkier polyaromatic terminal fragments lead to the formation of π-stacked supramolecular assemblies 6-10, respectively, in yields of 50-80 %. These derivatives have been characterized by multinuclear NMR spectroscopic analysis and X-ray diffraction studies. Their solid-state structures show the selective formation of U-shaped supramolecular assemblies in which two monotopic π-conjugated systems present large (6, 7 , and 9) or medium (8 and 10) intramolecular π overlap, thus revealing π -π interactions. These assemblies self-organize into head-to-tail π-stacked dimers that in turn self-assemble to afford infinite columnar π stacks. The ature, extent, and complexity of the intermolecular contacts within the head-to-tail π-stacked dimer depend on the nature of the terminal polyaromatic fragment carried by the cyano-capped monotopic ligand, but it does not alter the result of the self-assembling process. These results demonstrate that the dinuclear molecular clip A that bears short metal-metal distances allows selective supramolecular assembly processes driven by the formation of intra- and intermolecular short π-π interactions in the resulting self-assembled structures; thus, demonstrating that their shape is not only dictated by the symmetry of the building blocks. This approach opens perspectives toward the formation of extended π-stacked columns based on dissymmetrical and functional π-conjugated systems.

Full text of DOI:10.1002/chem.201403758

DOI: 10.1002/chem.201403758
Full Paper
&
Supramolecular Chemistry
Dissymmetrical U-Shaped p-Stacked Supramolecular Assemblies
I
by Using a Dinuclear Cu Clip with Organophosphorus Ligands
and Monotopic Fully p-Conjugated Ligands
Mehdi El Sayed Moussa, Kevin Guillois, Wenting Shen, Rꢀgis Rꢀau, Jeanne Crassous,* and
[a]
Christophe Lescop*
I
Abstract: Reactions between the U-shaped binuclear Cu
nature, extent, and complexity of the intermolecular con-
tacts within the head-to-tail p-stacked dimer depend on the
nature of the terminal polyaromatic fragment carried by the
cyano-capped monotopic ligand, but it does not alter the
result of the self-assembling process. These results demon-
strate that the dinuclear molecular clip A that bears short
metal–metal distances allows selective supramolecular as-
sembly processes driven by the formation of intra- and inter-
molecular short p–p interactions in the resulting self-assem-
bled structures; thus, demonstrating that their shape is not
only dictated by the symmetry of the building blocks. This
approach opens perspectives toward the formation of ex-
tended p-stacked columns based on dissymmetrical and
functional p-conjugated systems.
complex A that bears short metal–metal distances and the
cyano-capped monotopic p-conjugated ligands 1–5 that
carry gradually bulkier polyaromatic terminal fragments lead
to the formation of p-stacked supramolecular assemblies 6–
1
0, respectively, in yields of 50–80%. These derivatives have
been characterized by multinuclear NMR spectroscopic anal-
ysis and X-ray diffraction studies. Their solid-state structures
show the selective formation of U-shaped supramolecular
assemblies in which two monotopic p-conjugated systems
present large (6, 7, and 9) or medium (8 and 10) intramolec-
ular p overlap, thus revealing p–p interactions. These assem-
blies self-organize into head-to-tail p-stacked dimers that in
turn self-assemble to afford infinite columnar p stacks. The
Introduction
cal issue. For example, the formation of infinite p-stacked
arrays is of major importance for the manufacture of efficient
organic field effect transistors (OFETs) because long-range in-
termolecular p overlap between the conjugated systems in-
In recent years, studies focused on the synthesis and physical
properties of many oligomeric and polymeric p-conjugated or-
ganic systems have paved the way toward advanced materials
for the development of new optoelectronic devices (light-emit-
ting diodes, field-effect transistors, photovoltaic cells, and so
forth) with enhanced physical properties, low-energy con-
[3]
creases the charge-carrier mobility. To achieve the formation
of such infinite p-stacked molecular networks, noncovalent
[
4]
[5]
weak secondary forces, such as p–p, hydrogen-bonding,
[6]
[7]
amphiphilic, or charge-transfer interactions and coordina-
[
1]
[8]
sumption, and ease of manufacture. In this area, the solid-
state organization of these p-conjugated molecules and the
nature and extent of the intermolecular interactions they share
are closely related to the photophysical properties, dimension-
ality, and morphology of the related material, thus strongly in-
fluencing the performance of the devices built from these ma-
tion bonds, have been utilized. However, most of these ap-
proaches require long and sophisticated molecular engineering
of the organic p systems in a case-by-case basis, which de-
creases the accessibility of these molecular materials and sig-
nificantly increases their cost. Therefore, the development of
a general and reliable synthetic approach to obtain long-range
p stacking for a large variety of p-conjugated systems is still
a current subject of scientific interest.
[
2]
terials. Therefore, the ability to control the long-range supra-
molecular organization of p-conjugated chromophores is a criti-
In this field, we have previously described the coordination-
driven supramolecular synthesis (also called “directional-bond-
[
a] Dr. M. El Sayed Moussa, Dr. K. Guillois, Dr. W. Shen, Prof. R. Rꢀau,
Dr. J. Crassous, Dr. C. Lescop
[9]
ing approach”) of a series of p-stacked supramolecular rec-
[10]
tangles C obtained from the reaction of homoditopic and
symmetrical rigid organic p-conjugated linkers with dinuclear
Institut des Sciences Chimiques de Rennes
UMR 6226 CNRS, Universitꢀ de Rennes 1
Campus de Beaulieu, 35042 Rennes Cedex (France)
Fax: (+33)2-23-23-69-39
E-mail: christophe.lescop@univ-rennes1.fr
jeanne.crassous@univ-rennes1.fr
I
[11]
Cu U-shaped molecular clips A based on the 2,5-bis(2-pyri-
[12]
dyl)phosphole ligand B (Scheme 1). This synthetic method is
very versatile, which has been demonstrated
[10b]
by the possi-
bility of a large variation of the p cores (oligo(para-phenylene-
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201403758.
vinylene)s, oligo(phenylene)s, oligo(phenylethynylene)s), length
Chem. Eur. J. 2014, 20, 1 – 16
1
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
Scheme 2. Synthesis of derivatives 6–10.
[14]
gated systems was varied. Nevertheless, it was not possible
to discriminate which, if any, of the possible intermediates E
and F would be responsible for the selective formation of
supramolecular metallacycles C.
These observations triggered us to study the reaction of the
U-shaped molecular clip A with extended linear p-conjugated
systems that bear only one terminal nitrile coordination group
Scheme 1. Molecular structures of derivatives A and B, synthesis of the
supramolecular metallacycles C and D, and structures of the potential inter-
mediates E and F.
(
Scheme 2). Under these conditions, the monotopic extended
linear p-conjugated systems could substitute the acetonitrile-
labile ligands carried by A to afford a p-stacked analogue of in-
termediate F (Scheme 1). Thus, the preparation of original and
dissymmetrical p-stacked supramolecular assemblies would be
achieved. This approach could thereby give access to supra-
molecular assemblies that bear a variety of functions due to
the possible use of a monotopic p system that bears a large
scope of terminal aromatic moieties.
(
2.7–22.6 ꢂ), and geometry (linear, angular). Very importantly,
as the p surface of the p-conjugated linker is increased, these
p-stacked supramolecular rectangles self-assemble in the solid
[
10b]
state to afford infinite columnar p stacks.
The general char-
acter of this synthetic approach was extended to the reaction
À
of the metal-based linear linker [Au(CN)2] with molecular clip
A, thus giving rise to the “metal-rich” metallacycle
D
(
Scheme 1) that displays stabilizing intramolecular and inter-
Therefore, we focused our attention on the reaction of the
dissymmetrical monotopic cyano-capped p-conjugated ligands
[
13]
molecular aurophilic interactions.
In contrast, by using
I
Hg(CN) , which displays putative very weak mercurophilic in-
1–5 with the dinuclear Cu clip A (Scheme 2). Ligands 1 and 2
2
teractions, no selective supramolecular assembly process was
observed and supramolecular rectangles of type D were
formed together with linear oligomers and 1D coordination
were investigated to find out whether their reaction with the
I
U-shaped Cu molecular clip A could result in substitution of
I
the acetonitrile ligands coordinated to the Cu metal centers,
[
13]
polymers. This series of results suggested that the stabiliza-
tion of noncovalent interlinker lateral interactions (i.e., p–p
and aurophilic interactions) plays a key role in the coordina-
tion-driven synthetic process for driving the selective forma-
tion of metallacycles C and D. This assumption somehow does
not completely support the basic concepts of coordination-
driven supramolecular synthesis that rely on consideration of
the symmetry of the linking sites of the individual prepro-
grammed building blocks to allow a selective synthesis of
a complex assembly that bears a targeted shape.
thus affording p-stacked dimers of type F (Scheme 1). Ligand 3
was subsequently designed to study whether such substitution
and the self-assembly processes induced could be altered due
to the presence of a “large” lateral planar polyaromatic pyrene
terminal unit on the monotopic cyano-capped p-conjugated li-
gands treated with A. Finally, ligands 4 and 5 that bear the
bulkier nonplanar terminal carbo[4]helicene (also called ben-
zo[c]phenanthryl) groups were synthesized to probe the influ-
ence of a variation in the geometry and the steric congestion
of the monotopic cyano-capped p-conjugated ligands on the
result of their reaction with molecular clip A.
This consideration recently motivated us to explore the
[
14]
nature of the supramolecular intermediates that are formed
through such selective syntheses of metallacycles C and D to
obtain additional insight into the driving forces that govern Results and Discussion
these reactions and potentially access to new synthetic ap-
Synthesis and solid-state structures of monotopic
p-conjugated ligands 1–5
proaches to selectively afford new functional molecular materi-
als. Supramolecular intermediates E and F (Scheme 1) were
suggested on the basis of an experimental study in which the
stoichiometry of the molecular clip A versus “short” p-conju-
The synthesis of ligand 1 was achieved according to a reported
[15]
procedure. Ligand 2 was obtained in two synthetic steps
&
&
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
2
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
phonium bromide afforded olefin 18 as a mixture of Z and
[18]
E isomers, which was then subjected to photoirradiation to
produce the benzo[c]phenanthryl intermediate 19. The trime-
thylsilyl (TMS) protecting group was removed by using potassi-
um carbonate to give the ethynyl derivative 20, which was
treated with 4-bromobenzaldehyde according to a Sonogashira
coupling to produce 21. Ligand 5 was stereoselectively ob-
tained from a Wadsworth–Emmons reaction of 21 with the
phosphonate derivative 12.
Scheme 3. Synthesis of ligands 2 and 3. Reaction conditions: i) 4-Bromoben-
zaldehyde, [PdCl (PPh ], CuI, triethylamine, argon, 508C, overnight (80%);
ii) diethyl(4-cyanobenzyl)phosphonate (12), NaH, THF, argon, room tempera-
2
3 2
)
Ligands 1–5 were isolated as air-stable white (1 and 2),
orange (3), or yellow (4 and 5) powders, with solubilities that
were good (1 and 2) to moderate (3–5) in classical organic sol-
vents. These derivatives were characterized by NMR spectro-
scopic, mass-spectrometric, and elemental analysis. Of particu-
2 4
ture, overnight (54–90%); iii) DIBAL-H, toluene, H SO , argon, 308C (50%).
DIBAL-H=diisobutylaluminium hydride.
(Scheme 3). The first step of this synthesis was a Sonogashira
1
coupling between phenylacetylene and 4-bromobenzaldehyde
to afford derivative 11, which was subjected to a Wadsworth–
Emmons reaction with the previously described diethyl(4-cya-
lar interest are the H NMR chemical shifts of the H1 and H11
protons of the carbo[4]helicene derivatives (Scheme 4), which
are indicative of the formation of the ortho-fused polyaromatic
fragment (e.g., a singlet and doublet at d=9.35 and 9.17 ppm,
respectively, for 5). Ligands 2–5 were also characterized by UV/
Vis and fluorescence spectroscopic analysis (see the Support-
ing Information). Finally, the solid-state structures of ligands 3–
5 were determined by X-ray diffraction studies; despite several
crystallization attempts, extremely thin white crystalline nee-
dles unsuitable for X-ray diffraction studies were always ob-
tained for derivatives 1 and 2 (see Table 1). Homogeneous
batches of single crystals were obtained at room temperature
by diffusion of pentane into solutions of 3–5 in dichlorome-
thane. One asymmetrically independent molecule is present in
the unit cell of derivatives 3 and 5, whereas three asymmetri-
cally independent molecules and 2.5 dichloromethane solvent
molecules were observed in the solid-state structure of deriva-
tive 4. In all cases, the expected molecular structures were con-
firmed with an E conformation for all the C=C bonds.
[
10b]
nobenzyl)phosphonate (12),
thus leading to the stereose-
lective formation of the E isomer of ligand 2. Ligand 3 was syn-
thesized after three synthetic steps (Scheme 3). In the first
step, commercially available pyrene-1-carbaldehyde was en-
gaged in a Wadsworth–Emmons reaction with 12 to afford the
E isomer of derivative 14 stereoselectively. The nitrile group of
14 was reduced to an aldehyde group by using DIBAL-H, thus
giving derivative 15. Finally, a Wadsworth–Emmons reaction
between 15 and 12 produced the targeted ligand 3 as the
E,E isomer (Scheme 3).
Ligand
4
was isolated after
a
multistep synthesis
[16]
(
Scheme 4a) based on a Wittig reaction of derivative 16 and
In the case of ligand 3, the benzonitrile and pyrene groups
have a transoid orientation with regard to the central 1,4-sub-
stituted phenyl ring (Figure 1a). A torsion angle of approximat-
Scheme 4. Synthesis of ligands 4 and 5. Reaction conditions: i) Benzo[c]phe-
[
17]
nanthryl-3-yl-methylphosphonium bromide, nBuLi, THF, argon, À788C
then room temperature, overnight (50%); ii) hn, cat. I , toluene, overnight
80–90%); iii) naphthyl-2-yl-methylphosphonium bromide, nBuLi, THF, argon,
À788C then room temperature, overnight (90%); iv) CH Cl /MeOH, K CO
argon, 308C, overnight (95%); v) 4-bromobenzaldehyde, [PdCl (PPh ], CuI,
2
(
2
2
2
3
,
2
3 2
)
triethylamine, argon, 508C, overnight (60%); vi) 12, NaH, THF, argon, room
temperature, overnight (86%).
the previously described benzo[c]phenanthryl-3-ylmethylphos-
[
17a]
phonium bromide.
A mixture of the Z and E isomers was
[
18]
obtained and was subjected to photoirradiation with catalyt-
ic amounts of iodine, thus exclusively affording the E isomer
derivative 4 (Scheme 4a). Finally, ligand 5 was obtained after
five synthetic steps (Scheme 4b). The Wittig reaction between
the aldehyde derivative 17 and naphthyl-2-ylmethylphos-
Figure 1. Views of the X-ray structure (individual molecule and the solid-
state packing) of ligands a) 3, b) 4 (only the asymmetrically independent
molecule with noncoplanar moieties is shown), and c) 5.
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
3
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
Table 1. Crystal data and structure refinement for ligands 3–5 and assemblies 6–10 (after “squeeze” treatment for 4 and 6–10).
3
4
5
6·2BF
4
7
8·2BF
4
9·2BF
4
10
Formula
CCDC
C
33
H
21
N
C
105
H
62
C
10
N
3
C
35
H
21
N
C
94
H
76
B
2
Cu
2
F
8
N
6
P
2
C
94
H
72Cu
2
N
6
P
2
114 84 2 2 8 6 2 118 84 2 2 8 6 2 118 2 6 2
C H B Cu F N P C H B Cu F N P C H84Cu N P
1000686
431.51
5.8588(11)
7.6294(12)
48.737(9)
90
90
90
2178.5(7)
4
1000687
1365.58
36.646(5)
5.975(5)
38.071(5)
90
106.122(5)
90
8008(7)
4
1000688
455.53
16.156(4)
5.750(2)
25.921(56)
90
91.404(7)
90
2407(2)
4
899317
1652.25
899320
1474.60
1000689
1900.51
1000690
1948.55
1000691
1774.93
15.310(2)
22.858(5)
34.177(8)
78.610(8)
82.439(9)
73.741(8)
11219(4)
4
M
r
a [ꢂ]
b [ꢂ]
c [ꢂ]
a [8]
b [8]
g [8]
15.200(5)
16.218(5)
21.104(7)
86.006(12)
73.617(11)
75.269(10)
4827(3)
2
15.857(1)
16.381(1)
21.898(2)
85.376(3)
70.142(3)
76.364(3)
5199(1)
2
15.8929(6)
17.2540(8)
20.9818(11)
74.895(2)
70.393(2)
81.383(2)
5220.4(4)
2
15.280(2)
15.6671(18)
28.830(4)
79.958(5)
82.010(5)
77.823(4)
6605.3(15)
2
3
V [ꢂ ]
Z
1
calcd
1.316
1.133
1.257
1.137
0.942
1.209
0.980
1.051
À3
[Mgm ]
Crystal
system
Space
group
T [K]
orthorhombic
P212121
150(2)
monoclinic
monoclinic
triclinic
triclinic
triclinic
triclinic
triclinic
P21/c
P21/a
P-1
P-1
P-1
P-1
P-1
150(2)
150(2)
100(2)
150(2)
150(2)
150(2)
150(2)
l MoKa [ꢂ] 0.71073
0.71069
0.71069
0.71069
0.71069
0.71073
0.71073
0.71073
Crystal size 0.25ꢃ0.15ꢃ0.04 0.4ꢃ0.25ꢃ0.08 0.2ꢃ0.08ꢃ0.06 0.3ꢃ0.21ꢃ0.1
mm]
0.25ꢃ0.18ꢃ0.12 0.22ꢃ0.17ꢃ0.10 0.4ꢃ0.25ꢃ0.08
0.25ꢃ0.18ꢃ0.04
0.453
[
m (MoKa)
0.076
0.065
0.072
0.532
0.478
0.501
0.398
À1
[cm
]
F(000)
904
2852
952
1704
1532
1960
2008
3688
q limit [8]
Index
2.51–26.00
À7ꢀhꢀ7,
0.58–27.61
0.79–27.48
1.01–27.40
0.99–27.67
À20ꢀhꢀ17,
À21ꢀkꢀ19,
À28ꢀlꢀ28
94860
1.06–26.38
À19ꢀhꢀ19,
À21ꢀkꢀ21,
À26ꢀlꢀ26
45115
0.72–26.63
À19ꢀhꢀ18,
À19ꢀkꢀ19,
À36ꢀlꢀ36
94902
0.94–27.56
À19ꢀhꢀ19,
À29ꢀkꢀ29,
À44ꢀlꢀ34
77980
À47ꢀhꢀ29, À20ꢀhꢀ14, À19ꢀhꢀ19,
ranges hkl À9ꢀkꢀ 8,
À63ꢀlꢀ31
À7ꢀkꢀ4,
À49ꢀlꢀ49
34278
À5ꢀkꢀ7,
À33ꢀlꢀ32
11711
À20ꢀkꢀ20,
À27ꢀlꢀ26
42539
Reflects.
collected
Indep.
8360
4891
18371
5422
21529
23443
20774
27175
49215
reflects.
Reflects.
3586
3851
1867
12646
14085
8329
15015
10735
[
I>2s(I)]
Data/
4891/0/307
18371/0/931
5422/0/325
21529/0/1077
23443/0/937
20774/0/1208
27175/0/1241
49215/0/2295
restraints/
parameters
Goodness- 1.024
of-fit on F
0.769
0.963
0.932
1.013
0.875
0.956
0.692
2
Final R
R1=0.0537
R1=0.1133
R1=0.0885
R1=0.0607
R1=0.0887
R1=0.0762
R1=0.0685
R1=0.0854
indices
wR2=0.1053
wR2=0.2616 wR2=0.1899 wR2=0.1573
wR2=0.2488
wR2=0.1936
wR2=0.1871
wR2=0.2104
[
I>2s(I)]
R indices
all data)
R1=0.0829
wR2=0.1185
R1=0.2997
R1=0.2512
R1=0.0982
R1=0.1250
wR2=0.2780
1.574 and
À0.895
R1=0.1627
wR2=0.2198
0.675 and
À0.594
R1=0.1028
wR2=0.2022
0.682 and
À0.503
R1=0.2176
wR2=0.2401
0.487 and
À0.696
(
wR2=0.3328 wR2=0.2751 wR2=0.1727
0.445 and
À0.563
Largest diff 0.191 and
peak and
À0.229
0.221 and
À0.315
1.671 and
À0.696
À3
hole [eꢂ
]
ley 408 is observed between the mean planes of the pyrene
maximum deviation from the mean plane=0.1 ꢂ) and stilben-
three asymmetrically independent molecules ranges between
(
30.6 and 32.68, which is typical for carbo[4]helicene frag-
[19]
yl (maximum deviation from the mean plane=0.1 ꢂ) moieties,
which is likely to accommodate steric repulsion between the
protons H1(p)/H1(st) and H2(p)/H1(st) carried by the pyrene (p)
and stilbenyl (st) fragments, respectively (Scheme 3).
ments.
The solid-state structure of ligand 5 contains one
asymmetrically independent molecule that is planar along the
linear p-conjugated fragment, including the first phenyl ring of
the carbo[4]helicene moieties (maximum deviation from the
mean plane=0.3 ꢂ). The angle of helicity of the carbo[4]heli-
In the case of ligand 4, the observed geometric difference
between the three asymmetrically independent molecules is
mostly related to the torsion angle of the terminal benzonitrile
fragment and the central 1,4-substituted phenyl ring. In two of
these molecules (see Figure S2 in the Supporting Information),
this torsion angle is approximately 18, whereas the third mole-
cule bears a torsion angle of approximately 678 (Figure 1b).
The angle of helicity for the carbo[4]helicene fragments in the
[
19]
cene fragment in derivative 5 is approximately 31.08. Finally,
note that the space groups for 4 and 5 are centrosymmetric,
with racemic mixtures of P and M helices of the carbo[4]heli-
cene units. However, ligands 4 and 5 interconvert quickly in
[19]
solution at room temperature.
In the crystal packing of derivatives 3–5, columnar stacking
is observed with intermolecular distances (3.4–3.7 ꢂ) that
&
&
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
4
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
[
11]
reveal weak p–p interactions along these infinite columns
Figure 1). In the case of ligand 4, each of the three asymmetri-
served for the corresponding free molecular clip A and most
of the supramolecular assemblies obtained from A (see
(
[10,13]
cally independent molecules builds up one independent p-
stacked column. Note that for all the ligands, intermolecular
p–p contacts involve only limited fractions of neighboring
pyrene (3) or carbo[4]helicene (4 and 5) fragments, whereas
the cyano-capped linear p-conjugated portions are well isolat-
ed. These solid-state structures show that p–p stacking that in-
volves the fully p-conjugated systems of ligands 3–5 is not a fa-
vored arrangement. It is probably prohibited due to competi-
tive effects between weak interactions and steric constraints,
thus resulting in short contacts between fractions of the large
polyaromatic fragments rather than between their long linear
p-conjugated moieties. Therefore, a prediction of the long-
range solid-state organization of these asymmetric organic
p systems in regard to their molecular structures is difficult
and remains a major problem in the design of functional or-
ganic p-conjugated systems for material-science applications.
Table S1 in the Supporting Information).
These data indi-
I
cate that the structure of the Cu dimer, which features a bridg-
ing P-center, is maintained throughout these reactions. The
31
1
P{ H} NMR signals observed at room temperature are broad,
mostly due to the hemilabile behavior of ligand B in the coor-
dination sphere of the Cu centers of the {(Cu) (B) } frag-
ments. Therefore, the P{ H} NMR signals of these crude sol-
utions are not strongly indicative of the nature of the molecu-
lar structure present in solution because both the shape and
I
I
2
2
[11]
31
1
I
chemical-shift signals are mostly related to the {(Cu ) (B) } frag-
2
2
ment regardless of the nature and number of the cyano-
[
14]
capped ligands coordinated to the metal center. The crude
solutions obtained were subjected to diffusion of pentane
vapor and left to afford homogenous polycrystalline batches
of supramolecular assemblies 6–10 (Scheme 2) after several
days in moderate-to-good yields (ca. 50–80% yields for crystal-
line batches dried overnight under reduced pressure at room
31
1
temperature. The P{ H} NMR spectra recorded in CD Cl were
2
2
Synthesis and solid-state structures of the U-shaped
p-stacked supramolecular assemblies 6–10
mostly unchanged relative to the spectra recorded for the
1
mother solutions. The H NMR spectra in CD Cl2 presented
2
The p-conjugated ligands 1–5 were treated with the U-shaped
a single set of signals with a 2:1 integration ratio between the
I
Cu molecular clip A (Scheme 1) according to the following
signals assigned for the p-conjugated ligands 1–5 and the
I
I
common procedure (Scheme 2): The U-shaped Cu molecular
{(Cu)
2
(B)
} fragment. These signals are not significantly shifted
2
clip A was prepared in situ by the reaction in dichloromethane
at room temperature of one equivalent of ligand B (Scheme 1)
and one equivalent of [Cu(CH CN) ]·BF . One equivalent of li-
relative to those observed for the free building blocks. Notably,
no signals assigned to the acetonitrile ligands were observed.
These data strongly indicate substitution of the acetonitrile li-
3
4
4
I
gands 1–5 was subsequently added, thus resulting in clear
gands coordinated to the Cu centers of molecular clip A by
orange solutions that were stirred overnight at room tempera-
the cyano-capped monotopic p-conjugated ligands 1–5, but
do not allow us to propose a definitive molecular structure for
these species, which was finally obtained from single-crystal X-
ray diffraction studies. Single crystals of derivatives 6–10 were
31
1
ture. In all cases, the P{ H} NMR spectra of the mother solu-
tions exhibited a broad signal with a chemical shift at approxi-
mately d=+8 ppm (Table 2), which is similar to those ob-
3
1
1
Table 2. P{ H} NMR data, selected bond lengths [ꢂ], angles [8] and torsion angle for the supramolecular assemblies 6, 7, 8, 9, and 10.
3
1
Compd.
d P [ppm]
Intramolec.
p system to
p system
CuÀmP
CÀN
Cu···Cu
N-Cu-mP
Cu-mP-Cu
mP-Cu-Cu
Cu-NC-
CN-Cu-Cu-NC
distance [ꢂ]
6
7
8
9
+8.6 (brs)
+8.3 (brs)
+8.1 (brs)
+8.0 (brs)
+8.0 (brs)
3.3
3.4
3.6
2.2555(10)
2.053(3)
2.087(3)
2.6178(11)
2.5924(10)
2.6099(9)
2.6171(6)
82.41(9)
84.24(9)
67.32(4)
67.31(4)
67.76(5)
67.77(3)
53.39(3)
59.29(3)
2.004(3)
2.061(3)
33.5
34.2
29.9
35.9
2
.4395(11)
2.2711(13)
.4025(11)
2.039(4)
2.042(3)
83.17(9)
84.72(12)
53.93(3)
58.76(3)
1.986(4)
2.051(5)
2
2.2885(16)
2.2476(17)
2.034(5)
2.065(5)
85.03(15)
85.16(14)
54.25(4)
57.99(4)
2.014(6)
2.036(5)
[
b]
2
.7
3.5
2.3156(9)
2.045(2)
2.055(3)
84.00(8)
84.23(8)
54.99(2)
57.25(2)
1.985(3)
2.080(3)
2
.3777(9)
[
a]
1
0
3.3
–
2.2982(19)
2.396(2)
–
2.024(6)
2.047(5
–
2.020(5)
2.070(6)
2.6127(13)
–
2.6110(13)
84.08(16)
116.53(18)
–
84.33(17)
83.60(16)
67.61(6)
–
67.70(6)
54.42(5)
57.98(5)
–
58.22(6)
54.08(5)
2.050(7)
1.991(6)
–
2.024(7)
2.057(7)
34.8
–
38.4
3
2
.6
.7
[
b]
2.399(2)
2
.285(2)
[a] The first and second series of metric data are for conformers 10a and 10b, respectively. [b] Intramolecular distance for the CH–p interactions.
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
5
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
obtained at room temperature from diffusion of pentane into
solutions of the derivatives in dichloromethane.
larger than those measured in the U-shaped p-stacked assem-
blies 6 and 7. In each case, the two p ligands are located in
the vicinity of each other and short intramolecular p–p distan-
ces (ca. 3.3–3.4 ꢂ) are observed along a large part of their
backbone.
Derivatives 6 and 7 crystallize in the P-1 space group of the
triclinic system (Table 1). The asymmetric unit cells of 6 and 7
contain a dicationic assembly that results from the coordina-
I
tion of two ligands 1 or 2 onto a {(Cu) (B) } fragment
(
A very remarkable feature observed in the solid-state struc-
ture of most of the p-stacked supramolecular metallacycles of
type C is their self-organization within infinite p-stacked col-
2
2
À
Figure 2). The asymmetric units are completed by two BF4
[10]
umns,
thus affording a very general approach to the ar-
rangement of symmetrical linear p-conjugated organic systems
in infinite molecular networks in which all the p systems over-
lap. Interestingly, derivatives 6 and 7 that bear dissymmetrical
p-conjugated systems give also access to self-aggregated infin-
ite p-stacked columns in the solid state. Indeed, these deriva-
tives self-assemble into p-stacked dimers, which in turn stack
into infinite columns. Indeed, each dimer of 6 and 7 (Figure 2)
displays a head-to-tail arrangement with short contacts that in-
volve large fractions of the p-conjugated backbone of the
p walls (intermolecular distanceꢁ3.5–3.7 ꢂ), thus revealing ef-
ficient intermolecular p–p interactions (Figure 2). These dimers
of assemblies stack in turn on each other with “interdimer
p contacts” that involve a fraction of the p surface of the
neighboring ligands 1 or 2 (Figure 2). These infinite columns
are all oriented along the same direction in the bulk crystalline
À
solid state. Finally, the BF4 counterions and solvent molecules
in these assemblies are located in columns that run parallel to
À
the p-stacked columns. The BF4 counterions are mostly locat-
I
ed in the vicinity of the {(Cu ) (B) } units. Such localization of
Figure 2. Side and top views of the X-ray molecular structures of tetracat-
ionic derivatives 6 and 7; p-stacked head-to-tail dimers and infinite colum-
nar p stacks observed in the solid-state structure of derivatives 6 and 7 (the
2
2
À
the BF4 counterions and dichloromethane solvent molecules
is also observed in the other solid-state structures 8–10 (see
below).
solvent molecules and counterions have been omitted for clarity).
I
In conclusion, the simple reaction of the Cu molecular clip A
ions and 5.5 or 8 dichloromethane solvent molecules. All the
counteranions and cocrystallized solvent molecules are located
outside the self-assembled structure. Indeed, two cyano-
capped monotopic p systems have replaced the two acetoni-
trile ligands of A (Figure 2) in these derivatives, thus affording
U-shaped supramolecular assemblies. Metric data of the dicat-
with the dissymmetric cyano-capped p-conjugated monotopic
ligands 1 and 2 allows the preparation of new U-shaped supra-
molecular assemblies of type F (Scheme 1) that bear p-stacked
dimers and can subsequently self-organize within infinite p-
stacked columns. Converse to that observed within the p-
[10]
stacked supramolecular rectangles C, the two p-conjugated
systems are not forced to have a face-to-face organization
along all their p surface in assemblies of type F (Scheme 1).
Yet, p–p interactions within the self-assembled structures and
intermolecular p–p interactions within infinite columnar
p stacks are still observed. This result highlights the interest in
using polymetallic precursors that bear such short metal–metal
contacts in coordination-driven supramolecular syntheses to
afford original stacked supramolecular assemblies.
I
ionic {(Cu ) (B) } cores are very similar to the measurements of
2
2
the corresponding molecular clip A and to the data generally
observed for the supramolecular assemblies obtained from A
[10–14]
(
see Table 2 and Table S2 in the Supporting Information).
Within assembly 6, one of the ligands 1 is almost fully planar
maximum deviation from the mean plane=0.3 ꢂ); however,
(
the second p ligand is not fully planar because a twist angle of
approximately 27.18 is observed between the terminal phenyl
ring and the remaining planar part (maximum deviation from
the mean plane for the planar fragment=0.1 ꢂ) of this ligand.
Conversely, the two ligands 2 in derivative 7 are almost planar
These results prompted us to study the reaction of molecu-
lar clip A with other linear p-conjugated systems that bear one
cyano moiety as a terminal coordination group. Therefore, we
investigated the reaction of A with ligand 3 that bears
a pyrene moiety, thus affording derivative 8 (Scheme 2). In this
case, our interest was to probe the generality of such supra-
molecular synthetic processes toward p-stacked assemblies of
dissymmetrical p-conjugated systems. Will the presence of
a large planar polyaromatic group at the end of the linear
monotopic p-conjugated systems alter the result of the self-as-
sembling processes observed as ligands 1 and 2 undergo reac-
(maximum deviation from the mean planes for both ligands
2
=0.2 ꢂ; Figure 2). In both assemblies 6 and 7, the two p-con-
jugated ligands are not strictly parallel to each other (angle be-
tween the main planes of the two p systems=16.1 and 5.98
for 6 and 7, respectively) and are not pointing in the same di-
[20]
rection (Figure 2), thus affording a coordination angle
6.9 and 20.28, respectively. Notably, the related coordination
angle of the acetonitrile ligands in A (39.38) is significantly
of
1
&
&
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
6
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
tion with A? X-ray single-crystal analysis performed on deriva-
tive 8 revealed that this compound crystallizes in the P-1 space
group of the triclinic system (Table 1). The asymmetric unit cell
contains a dicationic assembly 8 that results from the coordi-
into dimers upon their coordination to the dinuclear U-shaped
molecular clip A, thus also resulting in assemblies of type F
(Scheme 1). Interestingly, upon this coordination, one of the
two p systems turns out to be almost fully planar, contrary to
that observed in the free ligand 3 (Figure 1a). This outcome il-
lustrates how the coordination of organic p-conjugated sys-
tems on metal complexes can induce structural changes in
I
nation of the two ligands 3 on a {(Cu) (B) } fragment (Fig-
2
2
À
ure 3a) and is completed by two BF4 ions and four dichloro-
[21]
their backbone in the solid state.
The reason for such an intramolecular organization can be
explained by considering the solid-state organization. Indeed,
assembly 8 in the bulk crystal arranges in a head-to-tail
manner similar to compounds 6 and 7 to afford p-stacked
supramolecular dimers of 8 (Figure 3). The nature of the inter-
molecular p–p interactions in these dimers is more complex
than those observed for 6 and 7 (Figure 2). Indeed, p-ligands
3
, which are not planar (light gray in Figure 3), are located
close to each other in the dimers of assemblies 8, with their
stilbenyl moiety located mostly in the same plane. The pyrene
fragments, owing to these ligands, are located transoid to each
other when considering the symmetry of this whole aggregate
(
Figure 3). Ligands 3, which are almost planar, lie above and
below these p ligands. These latter ligands are involved along
all their p surface in p–p interactions (intra- and intermolecular
distancesꢁ3.5 ꢂ; Table 2) with the two “central” nonplanar p-
ligands 3, belonging to each of the two assemblies 8, involved
in this p-stacked dimer. Therefore, the overlap of the p systems
through p–p interactions that involves the pyrene fragments is
significantly larger in the head-to-tail dimers of 8 than if only
Figure 3. a) Side and top views of the X-ray molecular structure of tetracat-
ionic derivative 8 (the CH–p interactions between the two pyrene fragments
is highlighted by a dotted line). The solid-state structures of derivatives 8 as
b) p-stacked head-to-tail dimers and c) infinite columnar p stacks (the sol-
vent molecules and counterions have been omitted for clarity).
I
the p-stacked dimer of ligand 3 coordinated to the {(Cu) (B) }
2
2
core within the individual molecule 8 is considered (Figure 3a).
In other words, the relative organization of ligands 3 and their
conformations in the solid-state structure of 8 is likely the
result from a maximization of the energy stabilization afforded
by intra- and intermolecular p–p interactions. Notably, the
pending pyrene fragments, which are part of the nonplanar
central ligands 3, are not involved in intermolecular p-stacked
interactions, and the intramolecular CH–p interaction that is
observed is probably a secondary stabilizing interaction that
fits both with the geometric constraints that lie in the core of
ligand 3 and the general organization of the head-to-tail p-
dimer of 8. Similar to that observed for derivatives 6 and 7 in
a second stage (Figure 2), these head-to-tail dimers of 8 stack
on top of each other to form infinite columns (Figure 3c), in
which all the p systems share short p–p interactions that in-
volve a portion of the stylbenyl part of the planar ligand 3 (in-
termolecular distanceꢁ3.5 ꢂ; Table 2). Notably, the extent of
the p–p interactions in these infinite columnar p stacks is sig-
nificantly larger than in the solid-state structure of the free
ligand 3 (Figure 1a). This observation confirms the ability of
methane solvent molecules. During the reaction, the labile ace-
tonitrile ligands of A are replaced by ligand 3. The metric data
I
of the dicationic {(Cu ) (B) } core in this derivative do not
2
2
change significantly relative to those built up from molecular
clip A (see Table 2 and Table S2 in the Supporting Informa-
[
10–14]
tion).
Interestingly, in the solid-state structure of 8, the
two ligands 3 have different geometric features. One ligand
displays a torsion angle between the linear stilbenyl moiety
and the pyrene fragment (ca. 42.28), which is similar to the
angle observed for the free ligand (ca. 40.08; Figure 1a), where-
as the second ligand is almost planar (maximum deviation
from the mean plane of the ligand=0.2 ꢂ, torsion angle be-
tween the linear stilbenyl moiety and the pyrene fragment
[
20]
ꢁ
5.68). The coordination angle (ca. 21.08) is slightly larger
than the angles observed in assemblies 6 and 7, and the two
p ligands overlap in a parallel displaced arrangement only
along a portion of the linear and almost planar stilbenyl frag-
ments (intramolecular distance between the p wallsꢁ3.6 ꢂ,
torsion angle between the mean planes of the two stilbenyl
fragments=8.78; Figure 3). The two pyrene fragments are not
parallel (torsion angle between the mean planes of the two
planar pyrene fragments=44.18) and a CH–p interaction is ob-
served between these moieties (CH–p distanceꢁ2.7 ꢂ), thus
resulting in a cisoid arrangement of these polyaromatic groups
when considering the whole symmetry of the assembly. There-
fore, two cyano-capped extended p-conjugated systems that
bear terminal planar polyaromatic fragments can be organized
I
the {(Cu ) (B) } core to force a large variety of p systems to in-
2
2
[10]
teract through p–p interactions upon coordination.
This example illustrates that the presence of a terminal poly-
aromatic pyrene moiety in the core of the cyano-capped p-
I
conjugated ligand 3 treated with the U-shaped Cu dinuclear
clip A does not drastically change the result of the self-assem-
bling process observed with ligands 1 and 2. Notably, a similar
hierarchical self-assembling process occurs despite a complicat-
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
7
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
ed and somehow unpredictable set of inter- and/or intramolec-
ular p–p and CH–p interactions that rule out local organization
of the molecules. Substitution of the acetonitrile ligands of A
still affords new p-stacked dimers of 8 that aggregate in
a head-to-tail fashion within infinite columnar p stacks. There-
fore, the interest in the use of dinuclear clip A to direct the
solid-state supramolecular organization of dissymmetrical
p-conjugated systems upon coordination is confirmed.
In the next step, we examined whether the presence of
a bulkier and nonplanar extended p-conjugated system graft-
ed onto the cyano-capped linear p-conjugated fragment coor-
I
dinated to the {(Cu ) (B) } core could induce some perturbation
2
2
in the self-assembling processes observed so far. Thus, we fo-
cused our interest on ligands 4 and 5 that bear a terminal car-
bo[4]helicene fragment. Indeed, this ortho-fused polyaromatic
group is known to be nonplanar in the solid state as a result
of a steric congestion between the H1 and H11 protons
Figure 5. Side and top views of the X-ray molecular structure of the asym-
metrically independent molecules 10a and 10b observed in the solid-state
structure of derivative 10 (the CH–p interactions between the two pyrene
fragments is highlighted by a doted line). The p-stacked head-to-tail dimers
observed in the solid-state structure of derivatives 10a and 10b (the solvent
molecules and counterions have been omitted for clarity).
(
Scheme 4), thus leading to an angle of helicity of approxi-
[
19]
mately 308. In solution at room temperature, this carbo[4]he-
licene is flexible and interconverts easily between the P- and
[19]
M-helical conformers with an average planar geometry. Such
structural flexibility should favor the integration of carbo[4]he-
licene-terminated monotopic nonplanar p systems within self-
assembled supramolecular structures. The reaction of ligands 4
and 5 with molecular clip A afforded derivatives 9 and 10, re-
spectively (Scheme 2). Single crystals were obtained in good
yields for these two compounds and X-ray diffraction studies
ure 1b), a large fraction of the backbone of the two p ligands
4 present in assembly 9 is almost planar (maximum deviation
from the mean plane (including the carbon atoms of the p-
conjugated system, except the carbon atoms of the two final
rings of the carbo[4]helicene fragment)=0.2 ꢂ). The angle of
helicity for the carbo[4]helicene fragment ranges from 25.6 to
27.38 and is smaller than the angles observed in the solid-state
structure of the free ligand 4 (30.6–32.68). The coordination
angle (7.98; Figure 4b) is also significantly smaller than the
angles observed in assemblies 6–8. The two p ligands are
almost parallel and overlap in a face-to-face fashion along
a large part of their p walls (intramolecular p–p interaction
(Table 1) revealed that they both crystallise in the P-1 space
group of the triclinic system. The asymmetric unit cell of 9 con-
[20]
tains a dicationic assembly, which results from the coordination
I
of two ligands 4 to a {(Cu) (B) } fragment (Figure 4a) and is
2
2
ꢁ
3.5–3.6 ꢂ). Finally, the two carbo[4]helicene fragments have
a cisoid arrangement as observed in derivative 8 when consid-
ering the whole symmetry of assembly 9. Therefore, the p-con-
jugated systems of the two ligands 4 overlap with p–p interac-
tions along a large portion of their core within assembly 9. No-
tably, the structural diversity that was observed in the solid-
state structure of ligand 4 (three conformations were ob-
served; Figure 1b) is not found in assembly 9, which is an illus-
tration of how self-assembling processes can select a conformer
among those possible to drive a selective synthesis. Note also
that the bulk crystal is overall racemic (centrosymmetric space
group), with homochiral P/P-9 or M/M-9 assemblies. In the
bulk crystalline solid state, derivative 9 aggregates into col-
umns that are similar to those observed for derivatives 6 and 7
(Figure 2). These columns are based on heterochiral p-stacked
dimers of 9 (Figure 4) with a head-to-tail arrangement with
short contacts that involve a large part of the p surface of the
p ligands (intermolecular distanceꢁ3.5–3.6 ꢂ; Table 2), thus re-
vealing efficient intermolecular p–p interactions. In turn, these
p-stacked dimers of 9 self-assemble with fractions of their
p walls involved in p–p interactions, thus leading to the
formation of infinite p-stacked columns (Figure 4).
Figure 4. a) Side and top views of the X-ray molecular structure of derivative
. The solid-state structures of derivatives 9 as b) p-stacked head to tail
dimers and c) infinite columnar p-stacks (the solvent molecules and counter-
9
ions have been omitted for clarity).
À
completed by two BF4 ions and eight dichloromethane sol-
vent molecules. The asymmetric unit cell of 10 is more com-
plex and contains two asymmetrically independent assemblies
1
0a and 10b (which result from the coordination of ligand 5
I
À
to a {(Cu) (B) } unit), four BF ions and ten dichloromethane
2
2
4
solvent molecules (Figure 5a). In assembly 9, the metric data
I
related to the {(Cu) (B) } core are not altered after the substitu-
2
2
tion of the two acetonitrile ligands of A by ligands 4 (see
[10,11,13,14]
Table 2 and Table S2 in the Supporting Information).
Converse to the solid-state structure of the free ligand 4 (Fig-
The two asymmetrically independent assemblies 10a and
10b observed in the X-ray structure of derivative 10 are differ-
&
&
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
8
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
ent due to the relative orientation of the two ligands 5. As ob-
served in the previously described assemblies 6–9, no signifi-
dimers of 10a and 10b aggregate with each other with signifi-
cant p overlap (intermolecular distance=3.3–3.6 ꢂ), thus yield-
ing infinite p-stacked columns alternating dimers of 10a and
10b (dark gray and light gray, respectively, in Figure 6).
I
cant metric changes occured in the {(Cu ) (B) } cores in both
2
2
conformers (see Table 2 and Table S2 in the Supporting Infor-
[
10–14]
mation).
The molecular organization observed in 10a is
quite similar to that of derivative 9 as the p systems of the
two ligands 5 are almost planar and parallel (maximum devia-
tion from the mean planes=0.2 ꢂ, including the carbon atoms
of the p-conjugated system, except the carbon atoms of the
two final rings of the carbo[4]helicene fragment). The angle of
helicity ranges from 26.0 to 32.28, which is comparable to that
[
20]
of the free ligand (318). The coordination angle in 10a is
7.48 and is larger than in derivative 9 (Figure 5). The p sy-
stems of the two ligands 5 in 10a overlap along a large part
of their p surfaces in parallel displaced arrangement
Figure 5). In the asymmetrically independent molecule 10b,
1
Figure 6. View of the infinite columnar p-stacked column observed in the
solid-state structure of derivative 10, which highlights the alternation of p-
stacked dimers of 10a and 10b.
a
(
I
the organization of ligands 5 coordinated to the {(Cu ) (B) }
2
2
fragments is similar to the organization observed in derivative
(Figure 3). One of the two ligands 5 is almost planar in its
linear part including the two first rings of the carbo[4]helicene
moiety (maximum deviation from the mean plane=0.1 ꢂ). The
angle of helicity of the carbo[4]helicene fragment of ligand 5 is
8
Hence, the reaction of monotopic cyano-capped extended
p-conjugated ligands 4 and 5 that bear large terminal nonpla-
nar carbo[4]helicene moieties with molecular clip A still affords
a hierachical self-assembly process that allows the formation of
p-stacked head-to-tail dimers, which in turn aggregate in infin-
ite columnar p stacks. Notably, the local organization of the
p systems in 10 is quite unpredictable, as observed for deriva-
tive 8 that bears a pyrene unit, which is probably a result of
a competition between the p–p interactions, CH–p interac-
tions, and steric congestion. In addition, it is difficult to ration-
alize why the monotopic ligand 4 that bears a triple-bond/
double-bond alternation and ligand 5 that bears a double-
bond/triple-bond alternation afford supramolecular p-stacked
aggregates with such local structural differences in their organ-
ization and, in particular, the formation in the solid state of ho-
mochiral p-stacked dimers (see derivative 9; Figure 4) versus
heterochiral p-stacked dimers (see derivative 10; Figure 5).
Nevertheless, as long as a supramolecular p-stacked dimer is
formed upon coordination of two monotopic p systems to the
3
0.98. Conversely, the second ligand 5 coordinated to the
I
{(Cu) (B) } unit is twisted twice along the p-conjugated back-
2 2
bone: once along the double bond and once along the triple
bond (twist angleꢁ34.6 and 23.68, respectively) of the linear
fraction of this ligand. The related carbo[4]helicene moiety dis-
plays an angle of helicity of 28.48. The coordination angle in
10b is 22.48 (Figure 5), and the two ligands 5 in 10b overlap
with an intramolecular p–p interaction (intermolecular dis-
tance=3.6 ꢂ), only at the level of the phenyl ring that bears
the coordinated nitrile group (Figure 5). No intramolecular p–p
interactions further occur between the backbone of the two li-
gands 5, but an intramolecular CH–p interaction (CH–p dis-
tanceꢁ2.6 ꢂ) between the two carbo[4]helicene moieties is
observed, thus resulting in a “T-shaped orientation” of these
two polyaromatic rings within assembly 10b (Figure 5). Note
that, converse to that observed in the case of derivative 9, the
two p-stacked dimers 10a and 10b are P/M-heterochiral ag-
gregates, which are organizations that certainly do not favor
good p overlap between the p-conjugated fragments of li-
I
{(Cu) (B) } unit, a similar aggregation of these dimers occurs
2
2
that affords infinite p-stacked columns in the solid state. Re-
markably, better p overlap between the individual p systems is
also always observed in these cases upon complexation rela-
tive to the solid-state structure of the free ligands 4 and 5,
a fact that is particularly striking in the case of assembly 9
(Figure 4) versus the free ligand 4 (Figure 1).
I
gands 5 coordinated on the {(Cu ) (B) } unit. Interestingly, the
2
2
bulk solid-state organization of derivative 10 also exhibits infin-
ite columnar p stacks despite such a structural diversity in
these two asymmetrically independent molecules. Indeed,
both derivatives 10a and 10b form head-to-tail p-stacked
dimers with similar intermolecular interactions as derivatives 9
and 8, respectively. In the case of 10a, large overlap between
the p walls occurs with intermolecular p–p distances of ap-
proximately 3.3–3.5 ꢂ. Concerning 10b dimers, the p systems
of the four ligands 5 share p–p interactions (intermolecular
distanceꢁ3.4–3.7 ꢂ; Table 2), and two of the carbo[4]helicene
moieties (part of the p systems located in the inner part of the
head-to-tail dimer; highlighted in light gray in Figure 5) are lo-
cated outside the p-stacked aggregate, but are connected
through intramolecular CH–p interactions, as in the case of the
pyrene moieties in derivative 8. Remarkably, these head-to-tail
Conclusion
We have shown that the reactions of the U-shaped molecular
clip A with the cyano-capped monotopic p-conjugated ligands
1–5 give a selective access to “U-shaped” p-stacked supra-
molecular assemblies 6–10 that form infinite columnar p stacks
in the solid state. Therefore, the very general ability of molecu-
lar clip A to assemble symmetric ditopic p-conjugated systems
within infinite p-stacked columns can be extended to the use
of monotopic dissymmetric p-conjugated systems. These re-
sults clearly highlight how the possibility of forcing the p-con-
jugated systems to share secondary stabilizing noncovalent p–
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
9
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
p interactions within the resulting self-assembled structures is
important in driving the outcome of the supramolecular as-
sembly processes based on the coordination of dinuclear mo-
lecular clips that bear short intermetallic distances. Indeed,
a similar hierarchical process occurs either if ditopic p-conju-
gated linkers, thus affording p-stacked supramolecular metalla-
sity of Rennes 1). Elemental analyses were performed by the
CRMPO (University of Rennes 1). UV/Vis/NIR spectroscopy was con-
ducted on a Varian Cary 5000 spectrometer.
[
17]
The intermediates benzo[c]phenanthrylphosphonium bromide,
[22]
4
-[(trimethylsilyl)ethynyl]benzaldehyde (17),
4-ethynylbenzalde-
[22]
[10b]
hyde, diethyl( 4-cyanobenzyl)phosphonate (12),
and 4-[(4-for-
[16]
mylphenyl)ethynyl]benzonitrile (16) were prepared according to
[
10a,b]
cycles,
or if monotopic p-conjugated linkers, thus affording
[23]
reported procedures. (E)-4-[2-(Pyren-1-yl)vinyl]benzonitrile (14)
U-shaped p-stacked supramolecular assemblies, undergo reac-
tion with precursor A. First, U-shaped assemblies are obtained
that involve strong intramolecular p–p interactions upon sub-
[24]
and (E)-4-[2-(pyren-1-yl)vinyl]benzaldehyde (15)
were prepared
according to modified procedures.
I
stitution of the acetonitrile ligands coordinated to the Cu ions
(E)-4-[4-(Phenylethynyl)styryl]benzonitrile (2)
of molecular clip A. Then, head-to-tail p-stacked dimers are
formed, which in turn aggregate in the solid state into infinite
p-stacked columns, along which significant intermolecular p–p
interactions occur. This series of results emphasizes the great
potential of molecular clip A that bears short intermetallic dis-
tances to allow original and selective supramolecular assembly
processes.
NaH (0.290 g, 12.12 mmol, 5 equiv) was added to a solution of the
phosphonate derivative 12 (0.614 g, 2.42 mmol) in THF (40 mL).
This mixture was stirred for 2 h at room temperature and 4-(phe-
Remarkably, the dissymmetrical cyano-capped monotopic p-
conjugated systems that are involved in these self-assembly re-
actions can bear a large structural variety, as demonstrated by
the use of derivatives 8–10 with large terminal planar (8) and
nonplanar (9 and 10) polyaromatic p-conjugated fragments.
Despite the fact that the local organization of these polyaro-
matic fragments is quite unpredictable, infinite columnar
p stacks are always obtained in the solid state. Therefore,
these series of results open interesting general synthetic per-
spectives to obtain molecular materials in which electron-rich,
electron-poor, or larger polyaromatic fragments, such as hexa-
peribenzocoronene or other “nanographene” fragments that
bear a cyano terminal function, would be organized into infin-
ite columnar p stacks. This class of material is indeed of inter-
est for the preparation of molecular materials for optoelectron-
ic devices in which efficient charge-transfer properties are re-
quested, such as in organic solar cells or field-effect transistors.
nylethynyl)benzaldehyde (11; 0.500 g, 2.42 mmol, 1 equiv) was
added. This mixture was stirred overnight at room temperature.
The crude mixture was filtered over silica, concentrated, and dried
under vacuum. Ligand 2 was obtained as an air-stable white
1
powder (0.665 g, 2.18 mmol, 90%). H NMR ( 400 MHz, CD Cl ): d=
2
2
3
7
.25 (AB system, 2H, nAB =30.9, J(H,H)=16.0 Hz; H6,H7), 7.40–7.44
(
m, 3H; H9,H17), 7.58–7.60 (m, 6H; H10,H15,H16), 7.69 ppm (AB
3
13
1
system, 4H, nAB =12.6, J(H,H)=8.4 Hz; H3,H4);
C{ H} NMR
(
100.6 MHz, CD Cl ): d=89.2 (s; C12), 90.7 (s; C13), 110.8 (s; C2),
2
2
118.9 (s; C1), 123.1 (s; C11), 123.2 (s; C14), 126.9 (s; C10), 127.0 (s;
C4), 127.6 (s; C6)128.4 (s; C9,C17), 131.4 (s; C7), 131.5 (s; C16),
132.0 (s; C15), 132.5 (s; C3), 136.4 (s; C8), 141.6 ppm (s; C5); HRMS
+
(
ESI): m/z calcd for C H N: 306.1283[M+H] ; found: 306.1282; ele-
23 16
mental analysis calcd (%) for C H N: C 90.46, H 4.95, N 4.59;
23 15
found: C 90.22, H 4.68, N 4.42.
4-{(E)-4-[(E)-2-(Pyren-1-yl)vinyl]styryl}benzonitrile (3)
NaH (0.024 g, 1.00 mmol, 5 equiv) was added to a solution of the
phosphonate derivative 12 (0.062 g, 0.24 mmol) in THF (15 mL).
This mixture was stirred for 2 h at room temperature and the alde-
Experimental Section
General remarks
All the experiments were performed in an argon atmosphere by
using standard Schlenk techniques. Commercially available re-
agents were used as received without further purification. The sol-
vents were freshly distilled under argon from sodium/benzophe-
none (THF) or phosphorus pentoxide (dichloromethane). Irradia-
tions were performed with a Heraeus TQ 150 mercury vapor lamp.
Preparative separations were performed by means of gravity
column chromatography on silica gel (Merck Geduran 60, 0.063–
hyde derivative 15 (0.071 g, 0.24 mmol, 1 equiv) was added to the
reaction mixture, which was stirred overnight at room temperature.
The crude mixture was filtered over silica, concentrated, and puri-
fied by recrystallization (eluent=CH Cl /pentane in 1:1 ratio).
2 2
Ligand 3 was obtained as an air-stable orange powder (0.057 g,
1
13
0
.200 mm) in columns that were 10–20 cm in length. H, C, and
P NMR spectra were recorded on Bruker DPX200, AM300, AV400,
3
1
1
13
1
3
or AV500 spectrometers. H and C NMR chemical shifts were re-
0.13 mmol, 54%). H NMR (400 MHz, CD
2
Cl
2
): d=7.30 (d, J(H,H)=
3
ported in parts per million (ppm) relative to Me Si as an external
16.2 Hz, 1H), 7.31 (AB system, 2H, nAB =42.4, J(H,H)=16.0 Hz),
7.69–7.63 (m, 7H), 7.75 (d, J(H,H)=8.0 Hz, 2H), 8.03 (m, 1H), 8.09
(s; 2H), 8.19 (d, J(H,H)=9.2 Hz, 1H), 8.22 (d, J(H,H)=8.0 Hz, 2H),
8.29 (d, J(H,H)=16.2 Hz, 1H), 8.39 (d, J(H,H)=8.0 Hz, 1H),
4
3
1
3
standard. P NMR downfield chemical shifts were expressed with
a positive sign (in ppm) relative to external 85% H PO and were
3
3
3
4
3
3
decoupled from the proton. Assignment of the proton atoms was
based on COSY experiments. Assignment of the carbon atoms was
based on HMBC, HMQC, and DEPT-135 experiments. High-resolu-
tion mass-spectrometry (HRMS) analysis was performed on a Varian
MAT 311 or ZabSpec TOF micromass instrument at CRMPO (Univer-
3
13
1
8.56 ppm (d, J(H,H)=9.2 Hz, 1H); C{ H} NMR (100.6 MHz, CD Cl ):
2
2
d=110.2 (s; Carom), 120.3 (s; CN), 122.9 (s; CHarom), 123.5 (s; CHarom),
125.1 (s; Carom), 125.4 (s; Carom), 125.4 (s; Carom), 125.5 (s; CHarom),
125.5 (s; CHarom), 125.9 (s; CHarom), 126.1 (s; CHarom), 126.4 (s; Carom),
&
&
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
10
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
126.7 (s; CHarom), 126.8 (s; CHarom), 127.2 (s; CHarom), 127.3 (s; CHarom),
127.4 (s; CHarom), 127.4 (s; Carom), 127.7 (s; CHarom), 128.4 (s; CHarom),
130.9 (brs; CHarom), 131.0 (s; Carom), 131.5 (s; CHarom), 131.8 (s;
air-stable white powder (1.217 g,
3.73 mmol, 90%, Z and E isomers).
1
H NMR (500 MHz, CDCl ): d=0.27 (s;
3
CHarom), 132.5 (s; CHarom), 132.6 (s; Carom), 132.6 (s; Carom), 138.1 (s;
9H; H trans), 0.30 (s; 7H; H cis), 6.74
c
c
3
Carom), 141.8 ppm (s; C ); HRMS (ESI): m/z calcd for C H N:
(AB system, 2H, nAB =71.98, J(H,H)=
12.0 Hz; H4,H5 cis), 7.21–7.36 (m, 8H;
Haroma, H4,H5 trans), 7.70–7.77 (m,
arom
33 22
+
4
32.1747 [M+H] ; found: 432.1743; elemental analysis calcd (%)
for C H N: C 91.85, H 4.91, N 3.25; found: C 91.62, H 4.84, N 3.39.
3
3
21
3
7
H; Harom), 7.78–7.82 (m, 1H; Harom),
.83–7.89 ppm (m, 3H; Harom);
(
E)-4-({4-[2-(benzo[c]phenanthren-2-yl)vinyl]phenyl}ethynyl)-
13
1
C{ H} NMR (100.6 MHz, CDCl ): d=0.0 (s; C cis or trans), 0.1 (s; C
c
3
c
benzonitrile (4)
cis or trans), 94.7 (s; C ), 94.7 (s; C ), 105.2 (s; C ), 105.3 (s; C ),
b
b
a
a
1
1
1
1
1
21.8 (s; C12), 122.2 (s; C12), 123.4 (s; CHarom), 126.0 (s; CHarom),
26.1 (s; CHarom), 126.2 (s; CHarom), 126.3 (s; CHarom), 126.4 (s; CHarom),
26.8 (s; CHarom), 126.9 (s; CHarom), 127.6 (s; CHarom), 127.6 (s; CHarom),
27.7 (s; CHarom), 128.0 (s; CHarom), 128.1 (s; CHarom), 128.3 (s; CHarom),
28.4 (s; CHarom), 128.5 (s; C), 128.6 (s; C), 128.9 (s; CHarom), 128.8 (s;
n-Butyllithium (2.5n in hexane, 0.48 mL, 1.20 mmol, 1.2 equiv) was
added to a solution of the benzo[c]phenanthryl-3-yl-methylphos-
phonium bromide (0.583 g, 1.00 mmol) in THF (40 mL) at À788C.
This mixture was warmed to room temperature and stirred for 2 h.
Derivative 15 (0.231 g, 1 mmol, 1 equiv) was added to the reaction
CHarom), 128.9 (s; CHarom), 131.0 (s; CHarom), 131.9 (s; CHarom), 132.0 (s;
C), 132.2 (s; C), 132.4 (s; CHarom), 132.7 (s; C), 133.2 (s; C), 133.5 (s;
C), 133.7 (s; C), 134.6 (s; CHarom), 137.5 (s; C), 137.5 ppm (s; C);
29
Si NMR (79.5 MHz, CDCl ): d=À17.71, À17.74 ppm; HRMS (ESI):
3
+
m/z calcd for C H Si: 327.1569 [M+H] ; found: 327.1567 (1 ppm).
23
23
Intermediate (benzo[c]phenanthren-2 ylethynyl)trimethyl-
silane (19)
A catalytic amount of iodine was added to a solution of the olefin
derivative 18 (0.4 g, 1.225 mmol) in toluene (750 mL). This mixture
was irradiated overnight, concentrated, and purified by column
chromatography on silica gel (eluent=heptane). Derivative 19 was
obtained as an air-stable colorless oil, which was washed several
times with ethanol to remove all traces of heptane, thus affording
mixture, which was stirred overnight at room temperature. The
crude mixture was concentrated and purified by column chroma-
tography on silica gel (eluent=AcOEt/heptane 5:95). Derivative 4
was obtained as a mixture of E and Z isomers, which was subjected
to photoirradiation in toluene in the presence of a catalytic
amounts of iodine. The E isomer of derivative 4 was obtained as an
a
1
white
powder
(0.375 g,
1
air-stable yellow powder (0.183 g, 0.40 mmol, 40%). H NMR
1
.156 mmol, 90%). H NMR (400 MHz,
3
(
1
400 MHz, CDCl ): d=7.40 (AB system, 2H, n =62.5, J(H,H)=
3
AB
CDCl ): d=0.36 (s; 9H; H ), 7.68 (dd,
3
3
c
3
6.3 Hz; H ,H ), 7.58 (d, 2H, J(H,H)=8.0 Hz; H ), 7.63–7.67 (m, 6H;
3
a
b
d
1
7
8
1
H, J(H,H)=7.0, J(H,H)=8.3 Hz; H2),
H ,H,H ), 7.67–7.71 (m, 1H; H9), 7.77 (ddd, 1H, J(H,H)=8.4, 6.9,
3
3
e
j
k
.71 (ddd, 1H, J(H,H)=6.9, J(H,H)=
3
3
1
5
.6 Hz; H10), 7.84 (d, 1H, J(H,H)=5.2 Hz; H5), 7.87 (d, 1H, J(H,H)=
Hz; H4), 7.91 (d, 1H, J(H,H)=8.0 Hz; H2), 7.95 (d, 1H, J(H,H)=8.
Hz; H6 or H7), 7.99–8.03 (m, 1H; H7 or H6), 8.04 (d, 1H, J(H,H)=
.0 Hz; H3), 8.07 (dd, 1H, J(H,H)=8.0, 1.6 Hz; H8), 9.18 (d, 1H,
J(H,H)=8.5 Hz; H11), 9.19 ppm (s; 1H; H1);
4
.0, J(H,H)=1.1 Hz; H9), 7.79 (ddd,
3
3
3
3
H,
J(H,H)=6.9,
J(H,H)=
3
4
8
.6, J(H,H)=1.5 Hz; H10), 7.84 (d, 1H,
8
3
J(H,H)=8.5 Hz; H6), 7.86 (d, 1H,
3
13
1
C{ H} NMR
3
3
3
3
J(H,H)=8.4 Hz; H5), 7.89 (d, 1H, J(H,H)=8.4 Hz; H4), 7.94 (d, 1H,
J(H,H)=8.5 Hz; H7), 7.97 (d, 1H, J(H,H)=8.3 Hz; H3), 8.06 (dd, 1H,
J(H,H)=8.0, J(H,H)=1.5 Hz; H8), 9.14 (d, 1H, J(H,H)=8.6 Hz;
(
100.6 MHz, CDCl ): d=88.7 (s; C ), 94.1 (s; C ), 111.5 (s; C), 118.5 (s;
3
3
h
g
i
Cm), 121.2 (s; Cl), 123.2 (s; C2), 126.0 (s; C9), 126.3 (s; C10), 126.6 (s;
Cd), 126.9 (s; C5), 127.1 (s; C4), 127.2 (s; C6 or C7), 127.5 (s; C1),
4
3
13
1
H11), 9.28 ppm (s; 1H; H1); C{ H} NMR (100.6 MHz, CDCl ): d=0.1
3
1
27.7 (s; C7 or C6), 127.8 (s; C11), 128.2 (s; C ), 128.3 (s; C), 128.7
b
(s; C ), 94.8 (s; C ), 106.0 (s; C ), 120.9 (s; C12), 126.1 (s; C9), 126.5
c b a
(
s; C8), 129.0 (s; C3), 130.3 (s; Carom), 130.7 (s; Carom), 130.8 (s; Carom),
(
1
s; C10), 126.7 (s; C6), 127.0 (s; Carom), 127.1 (s; C4), 127.8 (s; C5),
27.9 (s; C7,11), 128.5 (s; C3), 128.6 (s; C8), 128.8 (s; C2), 129.9 (s;
Carom), 130.2 (s; Carom), 131.3 (s; Carom), 131.8 (s; C1), 133.1 (s; Carom),
1
1
31.4 (s; Carom), 131.8 (s; Carom), 132.0 (s; C),132.1 (s; C ),132.2 (s; C ),
j k e
33.3 (s; Carom), 133.6 (s; Carom), 134.8 (s; Carom), 138.3 (s; Carom); ele-
mental analysis calcd (%) for C H N: C 92.28, H 4.65, N 3.07;
29
35
21
1
33.6 ppm (s; Carom); Si NMR (79.5 MHz, CDCl ): d=À17.61 ppm;
3
found: C 92.42, H 4.78, N 3.32.
+
HRMS (ESI): m/z calcd for C H Si: 325.1412 [M+H] ; found:
23
21
3
25.1415 (1 ppm).
Trimethyl({4-[2-(naphthalen-2-yl)vinyl]phenyl}ethynyl)silane
18)
(
Intermediate 2-ethynylbenzo[c]phenanthrene (20)
n-Butyllithium (1.66 mL, 4.14 mmol, 1 equiv) was added to a cold
K CO (1.300 g, 4.50 mmol, 2 equiv) was added to a solution of the
2
3
suspension of naphthyl-2-yl-methylphosphonium bromide (2.000 g,
silane derivative 19 (0.730 g, 2.25 mmol) in CH Cl /methanol (1:1,
2 2
4
.14 mmol) in THF (60 mL) at À788C. This mixture was warmed to
30 mL). This mixture was stirred overnight at 308C, neutralized
with diluted aqueous hydrochloric acid solution (1m), and extract-
room temperature and stirred for 2 h while the color turned slowly
deep red. This mixture was cooled to À788C and 4-[(trimethylsily-
l)ethynyl]benzaldehyde (17; 0.838 g, 4.14 mmol, 1 equiv) was
added to reaction mixture, which was warmed to room tempera-
ture, stirred overnight, and turned slowly orange–yellow. The crude
mixture was filtered over silica and concentrated, and the obtained
solid was dried under vacuum. Derivative 18 was obtained as an
ed with CH Cl2 (3ꢃ20 mL). The organic phases were collected,
2
dried over MgSO , and concentrated. Derivative 20 was obtained
4
as an air-stable colorless oil, which was washed several times with
ethanol to give a white powder (0.540 g, 2.137 mmol, 95%).
1
H NMR (400 MHz, CDCl ): d=3.26 (s; 1H; H ), 7.68 (ddd, 1H,
3
b
3
3
4
J(H,H)=6.9, J(H,H)=7.9, J(H,H)=1.2 Hz; H9), 7.73 (d, 1H,
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
11
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
3
3
J(H,H)=8.2 Hz; H2), 7.77 (ddd, 1H,
the obtained solid was dried under vacuum. Derivative 5 was ob-
tained as an air-stable yellow powder after washing with ethanol
3
4
J(H,H)=6.9, J(H,H)=8.6, J(H,H)=
3
1
1
8
8
8
8
8
.5 Hz; H10), 7.84 (d, 1H, J(H,H)=
(0.220 g, 0.48 mmol, 86%). H NMR (400 MHz, CDCl ): d=7.20 (AB
3
3
3
.6 Hz; H6), 7.87 (d, 1H, J(H,H)=
system, 2H, nAB =41.6, J(H,H)=16.3 Hz; H ,H ), 7.58 (d, 2H,
J(H,H)=8.4 Hz; H ), 7.61 (d, 2H, J(H,H)=8.4 Hz; H), 7.66–7.71 (m,
k j
g
h
3
3
3
.6 Hz; H5), 7.90 (d, 1H, J(H,H)=
3
3
.6 Hz; H4), 7.95 (d, 1H, J(H,H)=
5H; H9,H ,H ), 7.78 (d, 1H, J(H,H)=8.3 Hz; H2), 7.79 (ddd, 1H,
d e
3
3
3
3
3
3
3
4
.6 Hz; H7), 7.99 (d, 1H, J(H,H)=
J(H,H)=7.0, J(H,H)=8.5, J(H,H)=1.2 Hz; H10), 7.86 (d, 1H,
3
3
.2 Hz; H3), 8.06 (dd, 1H, J(H,H)=
J(H,H)=8.5 Hz; H6), 7.89 (d, 1H, J(H,H)=8.5 Hz; H5), 7.92 (d, 1H,
J(H,H)=8.5 Hz; H4), 7.96 (d, 1H, J(H,H)=8.5 Hz; H7), 8.03 (d, 1H,
J(H,H)=8.3 Hz; H3), 8.08 (d, 1H, J(H,H)=8.0 Hz; H8), 9.17 (d, 1H,
J(H,H)=8.5 Hz; H11), 9.35 ppm (s; 1H; H1);
4
3
3
7
9
.9 Hz, J(H,H)=1.5 Hz; H8), 9.11 (d, 1H, J(H,H)=8.6 Hz; H11),
.33 ppm (s; 1H; H1); C{ H} NMR (100.6 MHz, CDCl ) : d=77.6 (s;
C ), 84.6 (s; C ), 119.7 (s; C12), 126.1 (s; C9), 126.6 (s; C10), 126.7 (s;
13
1
3
3
13
1
C{ H} NMR
b
a
C6), 126.9 (s; Carom), 127.0 (s; C4), 127.7 (s; C11), 128.0 (s; C5,C7),
28.6 (s; C3,8), 128.7 (s; C2), 129.9 (s; Carom), 130.1 (s; Carom), 131.3
(100.6 MHz, CDCl ): d=89.9 (s; C ), 92.0 (s; C ), 110.8 (s; C), 119.0
(s; C ), 120.8 (s; C12), 123.5 (s; C ), 126.1 (s; C9), 126.6 (s; C10),
f m
3
b
a
l
1
(
(
(
s; Carom), 132.2 (s; C1), 133.3 (s; Carom), 133.6 ppm (s; Carom); HRMS
126.8 (s; C6), 126.8 (s; C or C ), 127.0 (s; C or C ), 127.0 (s; C), 127.1
j k j k
+
ESI): m/z calcd for C H : 353.1017 [M+H] ; found: 353.1010
(s; C4), 127.5 (s; C ), 127.8 (s; C11), 127.9 (s; C5), 128.0 (s; C7), 128.5
20
13
h
3 ppm).
(s; C2), 128.7 (s; C8), 128.7 (s; C3), 130.1 (s; Carom), 130.2 (s; Carom),
1
31.4 (s; Carom), 131.5 (s; C1), 131.7 (s; C ), 132.2 (s; C or C ), 132.5
g d e
(
1
s; Ce or C ), 133.1 (s; Carom), 133.6 (s; Carom), 136.2 (s; Carom),
d
4
-(Benzo[c]phenanthren-2-ylethynyl)benzaldehyde (21)
41.6 ppm (s; C ); HRMS (APCI): m/z calcd for C H N: 456.1747
arom 35 22
+
[M+H] ; found: 456.1745 (0 ppm); elemental analysis calcd (%) for
4
-Bromobenzaldehyde (0.220 g, 0.43 mmol), ethynyl derivative 20,
C35H21N: C 92.28, H 4.65, N 3.07; found: C 92.04, H 4.88, N 3.30.
[
PdCl (PPh ) ] (0.042 g, 0.02 mmol), and CuI (0.011 g, 0.02 mmol)
2 3 2
were dried in a Schlenk tube under vacuum for 2 h. Triethylamine
30 mL) was added to this mixture under argon, and the reaction
mixture was stirred at 508C overnight. The crude mixture was con-
(
General procedure of the synthesis of supramolecular
assemblies
centrated and purified by column
chromatography
on
silica
gel
A solution of the appropriate ligand (1 equiv) in CH Cl was added
2
2
(eluent=AcOEt/heptane 2:98). Deriv-
to a solution of ligand B (40 mg, 0.108 mmol) and [Cu(CH CN) ]·BF
4
3
4
ative 21 was isolated as a yellow
(
34 mg, 0.108 mmol) in CH Cl (10 mL). This reaction solution was
2 2
solid (0.250 g, 0.26 mmol, 60%).
stirred overnight and was left upon diffusion of pentane vapor into
the solution to afford the desired assembly as a batch of polycrys-
talline material. These batches of crystals were collected by filtra-
tion over paper and were dried under vacuum at 408C overnight.
The yields indicated correspond to the materials recovered after
this procedure and such crystallizations. Elemental analyses were
performed on samples obtained as described and after these mate-
rials had been left under vacuum overnight at 408C. Assemblies 6–
1
H NMR (400 MHz, CDCl ): d=7.67
3
3
3
(
ddd, 1H, J(H,H)=6.9, J(H,H)=7.9,
4
J(H,H)=1.2 Hz; H9), 7.75–7.78 (m,
3
3
H; H2,H ), 7.79 (ddd, 1H, J(H,H)=
d
3
4
3
6
.9, J(H,H)=8.6, J(H,H)=1.4 Hz; H10), 7.83 (d, 1H, J(H,H)=8.5 Hz;
H6), 7.87 (d, 1H, J(H,H)=8.6 Hz; H5), 7.88–7.91 (m, 3H; H4,H ),
3
e
3
3
7
.95 (d, 1H, J(H,H)=8.5 Hz; H7), 8.01 (d, 1H, J(H,H)=8.2 Hz; H3),
3
4
8
.06 (dd, 1H, J(H,H)=7.9, J(H,H)=1.4 Hz; H8), 9.13 (d, 1H,
1
0 were collected as red–orange powders.
3
J(H,H)=8.6 Hz; H11), 9.34 (s; 1H; H1), 10.04 ppm (s; 1H; H );
g
1
3
1
C{ H} NMR (100.6 MHz, CDCl ): d=89.2 (s; C ), 94.5 (s; C ), 120.1
3
b
a
Supramolecular assembly 6: By following the general procedure,
the reaction of B (40 mg, 0.108 mmol) and [Cu(CH CN) ]·BF
4
(
1
s; C12), 126.1 (s; C9), 126.6 (s; C10), 126.7 (s; C6), 127.0 (s; Carom),
27.1 (s; C4), 127.8 (s; C11), 128.0 (s; C7), 128.2 (s; C5), 128.4 (s;
C2), 128.7 (s; C8), 128.8 (s; C3), 129.6 (s; C ), 129.7 (s; Carom), 130.0
3
4
(34 mg, 0.108 mmol) with 1 (0.033 g, 0.108 mmol, 1 equiv) in
e
CH Cl (35 mL) afforded 6 as an air-stable orange solid after crystal-
2
2
(
1
s; Carom), 130.1 (s; Carom), 131.4 (s; Carom), 131.8 (s; C1), 132.2 (s; Cd),
33.4 (s; Carom), 133.6 (s; Carom), 135.4 (s; Carom), 191.4 ppm (s; C );
g
1
lization (0.005 g, 0.03 mmol, 62% yield). H NMR (200 MHz, CD Cl ):
2
2
+
d=1.43–1.66 (m, 4H; C=CH
CH
2
2
), 1.72–1.98 (m, 4H; C=CH
CH
2
),
2
HRMS (ESI): m/z calcd for C H O: 357.1279 [M+H] ; found:
27
17
2
.34–2.66 (m, 4H; C=CH ), 2.88–3.14 (m, 4H; C=CH ), 7.22 (AB
2 2
3
57.1281 (0 ppm).
3
system, 8H, nAB =26.9, J(H,H)=16.5 Hz; H6,H7,H12,H13), 7.33–7.48
m, 20H; H5 Py,H ,H16,H17), 7.52–7.69 (m, 24H; H3
(
Ph
3
Synthesis of ligand (E)-4-[4-(benzo[c]phenanthren-2-yl-
ethynyl)styryl]benzonitrile (5)
Py,H3,H4,H9,H10,H15),7.94 (dd, 4H, J(H,H)=7.6 Hz; H4 Py),
31
1
8
.50 ppm (brs; 4H; H6 Py); P{ H} NMR (CD Cl , 81 MHz): d=
2 2
8
.6 ppm
(brs);
elemental
analysis
calcd
(%)
for
NaH (0.070 g, 2.92 mmol, 5 equiv) was added to a solution of the
phosphonate derivative 12 (0.143 g, 0.56 mmol) in THF (60 mL).
This mixture was stirred for 2 h at room temperature and the alde-
hyde derivative 21 (0.200 g, 0.56 mmol, 1 equiv) was added to the
reaction mixture, which was stirred overnight at room temperature.
The crude mixture was filtered over silica and concentrated, and
C H B Cu F N P ·CH Cl : C 65.68, H 4.53, N 4.84; found: C 66.10, H
94
76
2
2
8
6
2
2
2
4
.60, N 4.36
Supramolecular assembly 7: By following the general procedure,
the reaction of B (40 mg, 0.108 mmol) and [Cu(CH CN) ]·BF
4
3
4
(34 mg, 0.108 mmol) with 2 (0.035 g, 0.108 mmol, 1 equiv) in
CH Cl (35 mL) afforded 7 as an air-stable red solid after crystalliza-
2
2
1
tion (0.065 g, 0.0375 mmol, 75% yield). H NMR (400 MHz, CD Cl ):
2
2
d=2.20 (brs; 4H; C=CH CH ), 2.56 (brs; 4H; C=CH CH ), 3.22 (brs;
2
2
2
2
4
4
H; C=CH ), 3.62–3.77 (m, 4H; C=CH ), 7.92 (AB system, 4H, n =
2 2 AB
3
2.5, J(H,H)=16 Hz; H6,H7), 8.03–8.12 (m, 20H; H5 Py,H ,H9,H17),
Ph
8
.24–8.34 (m, 24H; H3 Py,H3,H4,H10,H15,H16), 8.61 (dd, 4H,
3
31
1
J(H,H)=7.6 Hz; H4 Py), 9.16 ppm (brs; 4H; H6 Py); P{ H} NMR
&
&
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
12
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
(
(
6
CD Cl , 161.98 MHz): d=8.3 ppm (brs); elemental analysis calcd
%) for C H B Cu F N P ·2CH Cl : C 63.42, H 4.21, N 4.62; found: C
94 76 2 2 8 6 2 2 2
3.50, H 4.70, N 4.85.
was performed at 100 or 150 K on an APEX II Bruker-AXS (Centre
de Diffractomꢀtrie, Universitꢀ de Rennes 1, France) with MoKa radi-
ation (l=0.71073 ꢂ). Reflections were indexed, Lorentz-polariza-
tion corrected, and integrated by using the DENZO program of the
KappaCCD software package. The data-merging process was per-
2
2
Supramolecular assembly 8: By following the general procedure,
the reaction of (0.040 g, 0.11 mmol) and [Cu(CH CN) ]·BF
4
(
(
(
(
CH ), 2.88 (brs, 4H; C=CH ), 7.09 (d, 2H, J(H,H)=16.4 Hz; Hpyr),
7
7
[25]
formed by using the SCALEPACK program. Structure determina-
tions were performed by using direct methods with the solving
B
3
4
0.034 g, 0.11 mmol) with 3 (0.043 g, 0.11 mmol, 1 equiv) in CH Cl2
2
[26]
program SIR97, which revealed all the non-hydrogen atoms. The
35 mL) afforded 8 as an air-stable orange solid after crystallization
[27]
1
SHELXL program was used to refine the structures by using full-
0.046 g, 0.02 mmol, 46% yield). H NMR (400 MHz, CD Cl ): d=1.45
2
2
2
matrix least-squares based on F . Most of the non-hydrogen atoms
brs, 4H; C=CH CH ), 1.75 (brs, 4H; C=CH CH ), 2.41 (brs, 4H; C=
2
2
2
2
3
were refined with anisotropic displacement parameters (see the
Supporting Information for more details). Hydrogen atoms were in-
cluded in idealized positions and refined with isotropic displace-
ment parameters. In the crystal lattices of derivative 4, CH Cl sol-
2
2
3
.21 (d, 2H, J(H,H)=16.4 Hz; Hpyr), 7.23–7.26 (m, 14H; H5 Py,HPh),
3
.32 (d, 2H, J(H,H)=16.0 Hz; Hpyr), 7.50–7.55 (m, 14H; Hpyr), 7.64
3
(
d, 4H, J(H,H)=8.3 Hz; Hpyr), 7.65 (brs, 2H; H3 Py), 7.80 (br s, 4H;
2
2
vent molecules were found in addition to the three symmetrically
independent molecules found in the asymetric unit of the crystals
of this monotopic cyano-capped p-conjugated system. In the case
H4 Py), 7.91–8.00 (m, 6H; H ), 8.06–8.12 (m, 6H; Hpyr), 8.19(d, 2H,
pyr
3
3
J(H,H)=16.0 Hz; Hpyr), 8.26 (d, 2H, J(H,H)=8.0 Hz; H ), 8.37 (brs,
pyr
13
3
1
4
H; H6 Py), 8.44 ppm (d, 2H, J(H,H)=9.5 Hz; Hpyr); C{ H} NMR
of the cationic coordination complexes 6–10, the BF4À
counterions
(
100.6 MHz, CD Cl ): d=22.5 (brs; CH ), 28.7 (brs; CH ), 47.8 (brs;
2 2 2 2
and CH Cl solvent molecules were found in addition in the asy-
CH ), 110.2 (s; Carom), 123.2 (s; CHarom), 123.9 (s; CHarom), 125.2 (s;
2
2
2
metric unit of the crystals of these derivatives. In all cases, these
solvent molecules 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. Single crystals of
all these derivatives were always coated in paratone oil once re-
moved from the mother solution, mounted at low temperature
Carom), 125.4 (s; Carom), 125.5 (s; CHarom), 125.5 (s; CHarom), 125.8 (s;
CHarom), 126.3 (s; CHarom), 126.5 (s; CHarom), 127.9 (s; CHarom), 127.3 (s;
CHarom), 127.5 (s; CHarom), 127.7 (s; CHarom), 127.8 (s; CHarom), 127.8 (s;
CHarom), 127.9 (s; CHarom), 128.0 (s; CHarom), 130.0 (br s; CHarom), 131.3
(
s; Carom), 131.4 (s; CHarom), 131.9 (s; CHarom), 132.0 (s; Carom), 132.5 (s;
CHarom), 133.0 (s; CHarom), 133.0 (s; Carom), 136.3 (s; Carom), 139.1 (s;
Carom), 139.7 (br s; CHarom), 142.7 (s; CHarom), 150.4 ppm (br s;
3
1
1
(100 or 150 K) as quickly as possible on the diffractometer gionom-
CHarom); P{ H} NMR (CD Cl , 161.98 MHz): d=8.13 ppm (brs); ele-
2
2
eter, and X-ray data collection was performed at low temperature
to slow down this process. In most of the cases, X-ray crystal-struc-
ture resolution revealed that these solvent molecules are highly
disordered. In the case of derivatives 4 and 6–10 disordered CH Cl
mental analysis calcd (%) for C114H B Cu F N P ·CH Cl : C 69.57, H
84
2
2
8
6
2
2
2
4
.37, N 4.23; found: C 69.16, H 4.16, N 4.62.
2
2
Supramolecular assembly 9: By following the general procedure,
the reaction of B (0.040 g, 0.11 mmol) and [Cu(CH CN) ]·BF (0.03 g,
molecules occupy an important volume of the crystal cell and are
highly disordered. Correct modeling of the disorders of all these
CH Cl solvent molecules was not possible and we proceeded to
3
4
4
0
.11 mmol) with 4 (0.046 g, 0.11 mmol, 1 equiv) in CH Cl (35 mL)
2 2
2
2
afforded 9 as an air-stable orange solid after crystallization
1
a “squeeze” treatment to remove the scattering contribution of
these molecules, which could not be satisfactory modeled. In addi-
tion, in the case of the derivatives 7 and 10, the tetrafluoroborate
counterions were also severely disordered and were also involved
in the “squeeze” treatment. In the case of derivatives 3, 5, and 7–9,
anisotropic displacement parameters associated with the atoms of
the cationic coordination complexes of these compounds are satis-
factory. In the case of derivative 4, the crystals obtained were tiny
plates that were very sensitive to rapid desolvation of the included
solvent molecules and we could mount a single crystal with
a weak diffraction pattern associated with a large unit cell after
only several attemps, thus allowing the collection of a full data set.
As a consequence the X-ray data collection for derivative 4 is of
poor quality and some of the atoms had to be refined with iso-
tropic displacement parameters. In the case of assembly 6, one
part of the styryl moiety of one of the monotopic ligands 1 is dis-
ordered into two positions, for which relative occupancy was re-
fined. Some of the atoms involved in this disorder modeling have
rather high anisotropic displacement parameters (origin of an
ALERT A in the checkcif report). In the case of assembly 9, one of
the cyclohexyl rings fused to the phosphole ring of a B ligand is
disordered over two symetrical positions. Modeling of this disorder
was not possible and, consequently, this ring appears planar with
(
(
0.079 g, 0.02 mmol, 78% yield). H NMR (400 MHz, CD Cl ): d=1.43
2 2
brs, 4H; C=CH CH ), 1.76 (br s, 4H; C=CH CH ), 2.32 (brs, 4H; C=
2
2
2
2
CH ), 2.84–2.89(m, 4H; C=CH ), 7.12–7.33 (m, 32H), 7.41–7.61 (m,
2
2
1
9
1
8H), 7.74–7.88 (m, 8H), 7.93–8.02 (m, 2H), 8.35 (brs, 4H; H6 Py),
3
31
1
.09 ppm (d, 4H, J(H,H)=12.0 Hz; H1,H11); P{ H} NMR (CD Cl ,
2
2
61.98 MHz): d=8.0 ppm (brs); elemental analysis calcd (%) for
C118H B Cu F N P ·2CH Cl : C 68.03, H 4.19, N 3.97; found: C 68.50,
84
2
2
8
6
2
2
2
H 4.08, N 4.28.
Supramolecular assembly 10: By following the general procedure,
the reaction of (0.040 g, 0.11 mmol) and [Cu(CH CN) ]·BF
4
B
3
4
(
(
0.034 g, 0.11 mmol) with 5 (0.046 g, 0.11 mmol, 1 equiv) in CH Cl2
2
35 mL) afforded 10 as an air-stable orange solid after crystalliza-
1
tion (0.068 g, 0.02 mmol, 68% yield). H NMR (400 MHz, CD Cl ):
2
2
d=1.45 (brs, 4H; C=CH CH ), 1.75 (brs, 4H; C=CH CH ), 2.41 (brs,
2
2
2
2
4
H; C=CH2), 2.81–2.98(m, 4H; C=CH2), 7.04–7.27 (m, 12H;
H ,H ,H ,H ), 7.42–7.59 (m, 24H; H5 Py,H ,H9,H ,H ), 7.65 (dd, 4H,
h
g
k
j
Ph
d
e
3
J(H,H)=7.5 Hz; H3 Py), 7.74–7.84 (m, 16H; H4 Py,H2,H4–H7,H10),
.88 (d, 2H, J(H,H)=8.3 Hz; H3), 7.96 (d, 2H, J(H,H)=7.8 Hz; H8),
.36 (brs, 4H; H6 Py), 9.02 (d, 2H, J(H,H)=8.4 Hz; H11), 9.21 ppm
s; 2H; H1); P{ H} NMR (CD Cl , 161.98 MHz): d=8.0 ppm (brs); el-
2 2
3
3
7
8
(
3
3
1
1
emental analysis calcd (%) for C118H B Cu F N P ·2CH Cl : C 68.03,
84
2
2
8
6
2
2
2
H 4.19, N 3.97; found: C 67.64, H 4.10, N 4.02.
3
rather short interatomic distances for C sp atoms (origin of ALERTs
A in the checkcif report). Also, one of the terminal carbo[4]helicene
fragments bears quite high anisotropic displacement parameters
for several of its carbon atoms presumably due to disorder over
several positions closely located (this disorder was not possible to
model). Finally, in the case of assembly 10, a single crystal was col-
lected that was extremely sensitive to rapid desolvation of the in-
X-ray crystallographic study
Single crystals suitable for X-ray crystal analysis were obtained by
slow diffusion of pentane vapors into a solution of derivatives 3–
1
0 in CH Cl at room temperature. Single-crystal data collection
2 2
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
13
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
cluded solvent molecules; therefore, we could mount a single crys-
tal with a weak diffraction pattern associated with a large unit cell,
thus allowing the collection of a full data set, only after several at-
tempts. As a consequence, the X-ray data collection for derivative
Hagele, G. Scalia, R. Judele, E. Kapatsina, S. Sauer, A. Schreivogel, M.
Tosoni, Angew. Chem. 2007, 119, 4916–4973; Angew. Chem. Int. Ed.
2
007, 46, 4832–4887; d) S. Sergeyev, W. Pisula, Y. H. Geerts, Chem. Soc.
Rev. 2007, 36, 1902–1929; e) X. Feng, V. Marcon, W. Pisula, M. Hansen,
J. Kirkpatrick, F. Grozema, D. Andrienko, K. Kremer, K. Mꢅllen, Nat. Mater.
1
0 is of poor quality and some of the atoms had to be refined
2
009, 8, 421–426; f) D. Wu, W. Pisula, V. Enkelmann, X. Feng, K. Mꢅllen,
with isotropic displacement parameters while other atoms were as-
sociated with rather high anisotropic displacement parameters.
Table 1 gives the crystallographic data for derivatives 3–10, eventu-
ally obtained after the “squeeze” treatment. Table S1 (see the Sup-
porting Information) gives the crystallographic data for derivatives
J. Am. Chem. Soc. 2009, 131, 9620–9621; g) P. K. Madathil, J.-G. Lim, T.-
D. Kim, D. Beckmann, A. Mavrinskiy, W. Pisula, M. Baumgarten, K.
Mullen, K.-S. Lee, J. Nanosci. Nanotechnol. 2012, 12, 4269–4273.
4] a) E. A. Meyer, R. K. Castellano, F. Diederich, Angew. Chem. 2003, 115,
1244–1287; Angew. Chem. Int. Ed. 2003, 42, 1210–1250; b) T. Haino, Y.
[
ˇ
4
and 6–10 before the “squeeze” treatment. Atomic scattering fac-
Matsumoto, Y. Fukazawa, J. Am. Chem. Soc. 2005, 127, 8936–8937; c) Z.
tors for all the atoms were taken from International Tables for X-
Tomovi c´ , J. Dongen, S. J. George, H. Xu, W. Pisula, P. Leclꢄre, M. M. J.
Smulders; S. Feyter, E. W. Meijer, A. P. H. J. Schenning, J. Am. Chem. Soc.
[28]
ray crystallography.
CCDC 1000686, 1000687, 1000688, 899317, 899320, 1000689,
000690, and 1000691 contain the supplementary crystallographic
2
007, 129, 16190–16196; d) K. Ono, M. Yoshizawa, T. Kato, K. Watanabe,
M. Fujita, Angew. Chem. 2007, 119, 1835–1838; Angew. Chem. Int. Ed.
007, 46, 1803–1806; e) G. Fernꢆndez, E. M. Pꢀrez, L. Sanchez, N.
Martin, Angew. Chem. 2008, 120, 1110–1113; Angew. Chem. Int. Ed.
008, 47, 1094–1097; f) Y. Yamauchi, M. Yoshizawa, M. Fujita, J. Am.
1
2
data for derivatives 3–10 for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
2
Chem. Soc. 2008, 130, 5832–5833; g) M. H. C. J. van Houtem, R. Martꢇn-
Rapffln, J. A. J. M. Vekemans; E. W. Meijer, Chem. Eur. J. 2010, 16, 2258–
2271; h) I. Danila, F. Riobꢀ, F. Piron, J. Puigmartꢇ-Luis; J. D. Wallis; M. Li-
nares; H. ꢂgren, D. Beljonne, D. B. Amabilino, N. Avarvari, J. Am. Chem.
Soc. 2011, 133, 8344–8353; i) P. A. Korevaar, S. J. George, A. J. Mark-
voort, M. M. J. Smulders; P. A. J. Hilbers; A. P. H. J. Schenning, T. F. A. de
Greef, E. W. Meijer, Nature 2012, 481, 492–496; j) W. W. H. Wong, J. Sub-
biah, S. R. Puniredd, B. Purushothaman, W. Pisula, N. Kirby, K. Mꢅllen,
D. J. Jones; A. B. Holmes, J. Mater. Chem. 2012, 22, 21131–21137; k) L.
Chen, S. R. Puniredd, Y.-Z. Tan, M. Baumgarten, U. Zschieschang, V. En-
kelmann, W. Pisula, X. Feng, H. Klauk, K. Mꢅllen, J. Am. Chem. Soc. 2012,
134, 17869–17872; l) X. Guo, S. R. Puniredd, M. Baumgarten, W. Pisula,
K. Mꢅllen, J. Am. Chem. Soc. 2013, 135, 8404–8407; m) P. A. Korevaar,
T. F. A. de Greef, E. W. Meijer, Chem. Mater. 2014, 26, 576–586.
Acknowledgements
We thank the Ministꢄre de la Recherche et de l’Enseignement
Supꢀrieur, the CNRS, and the ANR (ANR-12-BS07-0004-METAL-
HEL-01 and ANR-12-IS07-0002 P-OPTOELECTR-MOLMAT).
Keywords: conjugation · noncovalent interactions · P ligands ·
polycycles · self-assembly
[
5] a) R. P. Sijbesma, F. H. Beijer, L. Brunsveld, B. J. B. Folmer, J. H. K. K.
Hirschberg, R. F. M. Lange, J. K. L. Lowe, E. W. Meijer, Science 1997, 278,
[
1] a) K. Mꢅllen, G. Wegner, Electronic Materials: The Oligomer Approach,
Wiley-VCH, Weinheim, 1998; b) L. Schmidt-Mende, A. Fechtenkotter, K.
Mꢅllen, E. Moons; R. H. Friend, J. D. MacKenzie, Science 2001, 293,
1601–1604; b) J. H. K. K. Hirschberg, L. Brunsveld, A. Ramzi, J. A. J. M.
Vekemans, R. P. Sijbesma, E. W. Meijer, Nature 2000, 407, 167–170; c) J.-
H. Fournier, T. Maris; J. D. Wuest, J. Org. Chem. 2004, 69, 1762–1775;
d) J. D. Wuest, Chem. Commun. 2005, 5830–5837; e) N. Malek, T. Maris;
M. Simard, J. D. Wuest, J. Am. Chem. Soc. 2005, 127, 5910–5916; f) K. E.
Maly, E. Gagnon, T. Maris; J. D. Wuest, J. Am. Chem. Soc. 2007, 129,
1119–1122; c) K. Mꢅllen, U. Scherf, Organic Light Emitting Devices: Syn-
thesis Properties and Applications, Wiley-VCH, Weinheim, 2006; d) S. W.
Thomas; G. D. Joly, T. M. Swager, Chem. Rev. 2007, 107, 1339–1386;
e) A. R. Murphy, J. M. J. Frꢀchet, Chem. Rev. 2007, 107, 1066–1096; f) S.
Gꢅnes, H. Neugebauer, N. S. Sariciftci, Chem. Rev. 2007, 107, 1324–
4
306–4322; g) L. R. MacGillivray, G. S. Papaefstathiou, T. Fri sˇ cˇ i c´ , T. D.
1
2
338; g) J. Roncali, P. Leriche, A. Cravino, Adv. Mater. 2007, 19, 2045–
060; h) T. F. A. De Greef, M. M. J. Smulders; M. Wolffs; A. P. H. J. Schen-
Hamilton, D.-K. Bucar, Q. Chu, D. B. Varshney, I. G. Georgiev, Acc. Chem.
Res. 2008, 41, 280–291; h) R. Matmour, I. D. Cat, S. J. George, W.
Adriaens; P. Leclꢄre, P. H. H. Bomans; N. A. J. M. Sommerdijk, J. C. Gielen,
P. C. M. Christianen, J. T. Heldens; J. C. M. Hest, D. W. P. M. Lwik, S. D.
Feyter, E. W. Meijer, A. P. H. J. Schenning, J. Am. Chem. Soc. 2008, 130,
ning, R. P. Sijbesma, E. W. Meijer, Chem. Rev. 2009, 109, 5687–5754; i) Y.-
J. Cheng, S.-H. Yang, C.-S. Hsu, Chem. Rev. 2009, 109, 5868–5923;
j) D. C. Bruce, D. O’Hare, R. I. Walton, Molecular Materials, Wiley-VCH,
Weinheim, 2010; k) W. Hu, Z. Bao, K. Mullen, J. Mater. Chem. 2012, 22,
14576–14583; i) R. Abbel, C. Grenier, M. J. Pouderoijen, J. W. Stouwdam,
4134–4138.
P. Leclꢄre, R. P. Sijbesma, E. W. Meijer, A. P. H. J. Schenning, J. Am. Chem.
Soc. 2009, 131, 833–843; j) T. Fri sˇ cˇ i c´ , L. R. MacGillivray, Chem. Commun.
[
2] a) E. W. Meijer, A. P. H. J. Schenning, Nature 2002, 419, 353–354;
b) F. J. M. Hoeben, P. Jonkheijm, E. W. Meijer, A. P. H. J. Schenning, Chem.
Rev. 2005, 105, 1491–1546; c) A. P. H. J. Schenning, E. W. Meijer, Chem.
Commun. 2005, 3245–3258; d) C.-M. Chou, S.-L. Lee, C.-H. Chen, A. T.
Biju, H.-W. Wang, Y.-L. Wu, G.-F. Zhang, K.-W. Yang, T.-S. Lim, M-J. Huang,
P.-Y. Tsai, K.-C. Lin, S.-L. Huang, C.-H. Chen, T.-Y. Luh, J. Am. Chem. Soc.
2
009, 773–775; k) A. Llanes-Pallas; C.-A. Palma, L. Piot, A. Belbakra, A.
Listorti, M. Prato, P. Samor, N. Armaroli, D. Bonifazi, J. Am. Chem. Soc.
2
2
009, 131, 509–520; l) Z. Li, F. W. Fowler, J. W. Lauher, J. Am. Chem. Soc.
009, 131, 634–643; m) T. S. J. George, R. de Bruijn, Z. Tomovic, B. va-
n Averbeke, D. Beljonne, R. Lazzaroni, A. P. H. J. Schenning, E. W. Meijer,
J. Am. Chem. Soc. 2012, 134, 17789–17796; n) T. Mes; S. Cantekin,
D. W. R. Balkenende, M. M. M. Frissen, M. A. J. Gillissen, B. F. M. de Waal,
I. K. Voets; E. W. Meijer, A. R. A. Palmans, Chem. Eur. J. 2013, 19, 8642–
2
2
009, 131, 12579–12585; e) B. R. Crenshaw, C. Weder, Chem. Mater.
003, 15, 4717–4724; f) M. A. Summers; G. C. Bazan, S. K. Buratto, J.
Am. Chem. Soc. 2005, 127, 16202–16206; g) R. Yang, A. Garcia, D. Kor-
ystov, A. Mikhailovsky, G. C. Bazan, T.-Q. Nguyen, J. Am. Chem. Soc.
8649;
2
006, 128, 16532–16539; h) R. Davis; N. S. S. Kumar, S. Abraham, C. H.
Suresh, N. P. Rath, N. Tamaoki, S. J. Das, J. Phys. Chem.C 2008, 112,
137–2146; i) N. S. S. Kumar, S. Varghese, N. P. Rath, S. J. Das, J. Phys.
[
6] a) M. Lee, J. W. Kim, S. Peleshanko, K. Larson, Y. S. Yoo, D. Vaknin, S. Mar-
kutsya, V. V. Tsukruk, J. Am. Chem. Soc. 2002, 124, 9121–9128; b) V.
Percec, M. Glodde, M. Peterca, A. Rapp, I. Schnell, H. W. Spiess; T. K.
Bera, Y. Miura, V. S. K. Balagurusamy, E. Aqad, P. A. Heiney, Chem. Eur. J.
2006, 12, 6298–6314; c) Y. Yamamoto, T. Fukushima, A. Saeki, S. Seki, S.
Tagawa, N. Ishii, T. Aida, J. Am. Chem. Soc. 2007, 129, 9276–9277;
d) W. S. Li, Y. Yamamoto, T. Fukushima, A. Saeki, S. Seki, S. Tagawa, H.
Masunaga, S. Sasaki, M. Takata, T. Aida, J. Am. Chem. Soc. 2008, 130,
8886–8887; e) Y. Yamamoto, G. X. Zhang, W. S. Jin, T. Fukushima, N.
Ishii, A. Saeki, S. Seki, S. Tagawa, T. Minari, K. Tsukagoshi, T. Aida, Proc.
Natl. Acad. Sci. USA 2009, 106, 21051–21056; f) M. A. J. Gillissen,
2
Chem. C 2008, 112, 8429–8437; j) J. Dong, K. M. Solntsev, L. M. Tolbert,
J. Am. Chem. Soc. 2009, 131, 662–670; k) F. E. Golling, M. Quernheim, M.
Wagner, T. Nishiuchi, K. Mullen, Angew. Chem. 2014, 126, 1551–1554;
Angew. Chem. Int. Ed. 2014, 53, 1525–1528; l) D. Niedzialek, V. Lemaur,
D. Dudenko, J. Shu, M. R. Hansen, J. W. Andreasen, W. Pisula, K. Mullen,
J. Cornil, D. Beljonne, Adv. Mater. 2013, 25, 1939–1947.
[
3] a) M.-H. Yoon, A. Facchetti, C. E. Stern, T. J. Marks, J. Am. Chem. Soc.
2
2
006, 128, 5792–5801; b) J. S. Wu, W. Pisula, K. Mꢅllen, Chem. Rev.
007, 107, 718–747; c) S. Laschat, A. Baro, N. Steinke, F. Giesselmann, C.
&
&
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
14
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
M. M. E. Koenigs; J. J. H. Spiering, J. A. J. M. Vekemans; A. R. A. Palmans;
I. K. Voets; E. W. Meijer, J. Am. Chem. Soc. 2014, 136, 336–343;
7] a) J. van Herrikhuyzen, A. Syamakumari, A. Schenning, E. W. Meijer, J.
Am. Chem. Soc. 2004, 126, 10021–10027; b) M. Treier, A. Liscio, J. M.
Mativetsky, M. Kastler, K. Mꢅllen, V. Palermo, P. Samori, NANOSCALE
[10] a) B. Nohra, S. Graule, C. Lescop, R. Rꢀau, J. Am. Chem. Soc. 2006, 128,
3520–3521; b) Y. Yao, W. Shen, B. Nohra, C. Lescop, R. Rꢀau, Chem. Eur.
J. 2010, 16, 7143–7163; c) A. I. Aranda Perez, T. Biet, S. Graule, T. Agou,
C. Lescop, N. R. Branda, J. Crassous; R. Rꢀau, Chem. Eur. J. 2011, 17,
1337–1351.
[
2
012, 4, 1677–1681.
[11] a) F. Leca, C. Lescop, E. Rodriguez-Sanz, K. Costuas; J.-F. Halet, R. Rꢀau,
Angew. Chem. 2005, 117, 4436–4439; Angew. Chem. Int. Ed. 2005, 44,
4362–4365; b) B. Nohra, E. Rodriguez-Sanz, C. Lescop, R. Rꢀau, Chem.
Eur. J. 2008, 14, 3391–3403.
[12] a) C. Hay, D. Le Vilain, V. Deborde, L. Toupet, R. Rꢀau, Chem. Commun.
1999, 345–346; b) C. Hay, M. Hissler, C. Fischmeister, J. Rault-Berthelot,
L. Toupet, L. Nyulaszi, R. Rꢀau, Chem. Eur. J. 2001, 7, 4222–4236.
[13] V. Vreshch, W. Shen, B. Nohra, S.-K. Yip, V.W-W. Yam, C. Lescop, R. Rꢀau,
Chem. Eur. J. 2012, 18, 466–477.
[
8] a) J.-M. Lehn, Supramolecular Chemistry, Concepts and Perspectives, VCH,
Weinheim, 1995; b) J.-P. Sauvage, Transition Metals in Supramolecular
Chemistry, Wiley and Sons; Chichester, 1994; c) A. El-ghayoury, L. Douce,
A. Skoulios; R. Ziessel, Angew. Chem. 1998, 110, 2327–2331; Angew.
Chem. Int. Ed. 1998, 37, 2205–2208; d) K. Binnemans; K. Lodewyckx, B.
Donnio, D. Guillon, Chem. Eur. J. 2002, 8, 1101–1105; e) J. Barberꢆ, R. Gi-
mꢀnez, N. Gimeno, M. Marcos; M. D. C. Pina, J. L. Serrano, Liq. Cryst.
2003, 30, 651–661; f) L. Douce, T. H. Diep, R. Ziessel, A. Skoulios; M. Cꢀ-
sario, J. Mater. Chem. 2003, 13, 1533–1539; g) M. Ruben, J. Rojo, F. J.
Romero-Salguero, L. H. Uppadine, J. M. Lehn, Angew. Chem. 2004, 116,
[14] B. Nohra, R. Rꢀau, C. Lescop, Eur. J. Inorg. Chem. 2014, 1788–1796.
[15] D. P. Flaherty, Y. Dong, J. L. Vennerstrom, Tetrahedron Lett. 2009, 50,
6228–6230.
3728–3747; Angew. Chem. Int. Ed. 2004, 43, 3644–3662; h) J.-Q. Jiang,
Z.-R. Shen, J. Lu, P.-F. Fu, Y. Lin, H.-D. Tang, H.-W. Gu, J. Sun, P. Xie, R.-B.
Zhang, Adv. Mater. 2004, 16, 1534–1539; i) M. Marcos; A. Omenat, J.
Barberꢆ, F. Durꢆn, J. L. Serrano, J. Mater. Chem. 2004, 14, 3321–3327;
j) D. M. Huck, H. L. Nguyen, B. Donnio, D. W. Bruce, Liq. Cryst. 2004, 31,
[16] C. Richardson, C. A. Reed, J. Org. Chem. 2007, 72, 4750–4755.
[17] D. A. Lightner, D. T. Hefelfinger, T. W. Powers; G. W. Frank, K. N. True-
blood, J. Am. Chem. Soc. 1972, 94, 3492–3497.
[18] a) Y. Shen, C.-F. Chen, Chem. Rev. 2012, 112, 1463–1535; b) S. Graule, M.
Rudolph, W. Shen, C. Lescop, J. A. G. Williams; J. Autschbach, J. Cras-
sous; R. Rꢀau, Chem. Eur. J. 2010, 16, 5976–6005; c) M. El Sayed Moussa,
M. Srebro, E. Anger, N. Vanthuyne, C. Roussel, C. Lescop, J. Autschbach,
J. Crassous, Chirality 2013, 25, 455–465.
[19] The angle of helicity is defined by the torsion angle measured between
the planes defined by the terminal phenyl rings; see: E. Anger, M. Ru-
dolph, L. Norel, S. Zrig, C. Shen, N. Vanthuyne, L. Toupet, J. A. G. Wil-
liams; C. Roussel, J. Autschbach, J. Crassous; R. Reau, Chem. Eur. J. 2011,
17, 14178–14198 and ref. [18b].
503–507; k) O. Maury, H. Le Bozec, Acc. Chem. Res. 2005, 38, 691–704;
l) M. C. Torralba, D. M. Huck, H. L. Nguyen, P. N. Horton, B. Donnio, M. B.
Hursthouse, D. W. Bruce, Liq. Cryst. 2006, 33, 399–407; m) U. Schlickum,
R. Decker, F. Klappenberger, G. Zoppellaro, S. Klyastskaya, M. Ruben, I.
Silanes; A. Arnau, K. Kern, H. Brune, J. V. Barth, Nano Lett. 2007, 7,
3813–3817; n) S. Graule, M. Rudolph, N. Vanthuyne, J. Autschbach, C.
Roussel, J. Crassous; R. Rꢀau, J. Am. Chem. Soc. 2009, 131, 3183–3185.
9] a) S. Leininger, B. Olenyuk, P. J. Stang, Chem. Rev. 2000, 100, 853–908;
b) R. S. Seidel, P. J. Stang, Acc. Chem. Res. 2002, 35, 972–983; c) G. J.;
Holliday, C. A. Mirkin, Angew. Chem. 2001, 113, 2076–2097; Angew.
Chem. Int. Ed. 2001, 40, 2022–2043; d) F. A. Cotton, C. Lin, C. A. Murillo,
Acc. Chem. Res. 2001, 34, 759–771; e) R. J. Puddephatt, Coord. Chem.
Rev. 2001, 216–217, 313–332; f) M. Fujita, M. Tominaga, A. Aoai, B.
Therrien, Acc. Chem. Res. 2005, 38, 369–378; g) N. C. Gianneschi, M. S.
Masar III, C. A. Mirkin, Acc. Chem. Res. 2005, 38, 825–837; h) S. J. Lee, W.
Lin, Acc. Chem. Res. 2008, 41, 521; for recent reviews and articles: i) B.
Therrien, Eur. J. Inorg. Chem. 2009, 2445–2453; j) B. H. Northrop, Y. R.
Zheng, K. W. Chi, P. J. Stang, Acc. Chem. Res. 2009, 42, 1554–1563;
k) P. J. Stang, J. Org. Chem. 2009, 74, 2–20; l) M. Yoshizawa, J. Kloster-
man, M. Fujita, Angew. Chem. 2009, 121, 3470–3490; Angew. Chem. Int.
Ed. 2009, 48, 3418–3438; m) Y. R. Zheng, P. J. Stang, J. Am. Chem. Soc.
[
[20] The coordination angle is defined by the torsion angle “C -Cu1-Cu2-C ”
A
B
where CA and CB are the carbon atoms in the para position of the
phenyl rings that attach the lateral p-conjugated systems to the con-
necting linear p-conjugated system.
[21] H. Chen, W. Delaunay, L. Yu, D. Joly, Z. Wang, J. Li, Z. Wang, C. Lescop,
D. Tondelier, B. Geffroy, Z. Duan, M. Hissler, F. Mathey, R. Rꢀau, Angew.
Chem. 2012, 124, 218–221; Angew. Chem. Int. Ed. 2012, 51, 214–217.
[22] B. W. Austin, N. Bilow, W. J. Kelleghan, K. S. Y. Lau, J. Org. Chem. 1981,
46, 2280–2286.
[23] M. Beinhoff, W. Weigel, M. Jurczok, W. Rettig, C. Modrakowski, I. Brudg-
am, H. Hartl, A. D. Schluter, Eur. J. Org. Chem. 2001, 3819–3829.
[24] A. Cirpan, H. P. Rathnayake, P. M. Lahti, F. E. Karasz, J. Mater. Chem. 2007,
17, 3030–3036.
2009, 131, 3487–3489; n) P. Jin, S. J. Dalgarno, J. L. Atwood, Coord.
Chem. Rev. 2010, 254, 1760–1768; o) R. Chakrabarty, P. S. Mukherjee,
P. J. Stang, Chem. Rev. 2011, 111, 6810–6918; p) Y. Inokuma, M. Kawano,
M. Fujita, Nat. Chem. 2011, 3, 349–358; q) H. Amouri, C. Desmarets; J.
Moussa, Chem. Rev. 2012, 112, 2015–2041; r) L. R. MacGillivray, Angew.
Chem. 2012, 124, 1136–1138; Angew. Chem. Int. Ed. 2012, 51, 1110 –
[25] Z. Otwinowski, W. Minor in Methods in Enzymology (Ed.: C. W. Carter, Jr.,
R. M. Sweet), Academic Press, New York, 1997, 276, 307.
[26] A. Altomare, M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, A.
Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna, J. of Applied Cryst.
1999, 32, 115.
1
112; s) Q. Sun, S. Sato, M. Fujita, J. Am. Chem. Soc. 2013, 135, 12497–
[27] G. M. Sheldrick, SHELX97, Program for the Refinement of Crystal Struc-
tures; University of Gçttingen, Germany, 1997.
[28] International Tables for X-ray Crystallography, Vol C, Kluwer, Dordrech,
1992.
12499; t) K. Harris; D. Fujita, M. Fujita, Chem. Commun. 2013, 49, 6703–
6712; u) Y. Fang, T. Murase, S. Sato, M. Fujita, J. Am. Chem. Soc. 2013,
135, 613–615; v) M. Yoneya, S. Tsuzuki, T. Yamaguchi, S. Sato, M. Fujita,
ACS Nano 2014, 8, 1290–1296; w) H. Takezawa, T. Murase, G. Resnati, P.
Metrangolo, M. Fujita, J. Am. Chem. Soc. 2014, 136, 1786–1788; x) T.
Sawada, H. Hisada, M. Fujita, J. Am. Chem. Soc. 2014, 136, 4449–4451;
y) J.-P. Ma, S.-Q. Wang, C.-W. Zhao, H.-Y. Wang, Y.-B. Dong, Chem.
Commun. 2014, 50, 4721–4724; z) L. Xu, L.-J. Chen, H.-B. Yang, Chem.
Commun. 2014, 50, 5156–5170.
Received: May 30, 2014
Published online on && &&, 0000
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
15
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
FULL PAPER
Stretching into infinity: A general ap-
proach to p-stacked dissymmetrical
supramolecular assemblies is described.
The reaction of a series of dissymmetri-
cal cyano-capped monotopic p-conju-
&
Supramolecular Chemistry
M. El Sayed Moussa, K. Guillois, W. Shen,
R. Rꢀau, J. Crassous,* C. Lescop*
&
& – &&
I
gated systems with a U-shaped Cu di-
Dissymmetrical U-Shaped p-Stacked
nuclear molecular clip results in the for-
mation of U-shaped p-stacked supra-
molecular assemblies that self-assemble
in the solid state along infinite columns
of interacting p systems, regardless of
the nature of the p-conjugated system
Supramolecular Assemblies by Using
I
a Dinuclear Cu Clip with
Organophosphorus Ligands and
Monotopic Fully p-Conjugated
Ligands
(
see picture).
&
&
Chem. Eur. J. 2014, 20, 1 – 16
www.chemeurj.org
16
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!