Synthesis of alternating metallocopolymers by chiral recognition

Article abstract of DOI:10.1002/chir.23128

We report the synthesis of chiral enantiopure polytopic bridging ligands, which may lead to the formation of metallosupramolecular polymers with zinc (II) as metal linker. We show that chiral C₂-symmetric bisoxazoline ligands are useful moieties to efficiently generate heterochiral complexes and thus polymeric entities. The corresponding metallopolymers were further characterized by powder X-ray diffraction (PXRD) to obtain information on the level of crystallinity of our different metallopolymers.

Full text of DOI:10.1002/chir.23128

Received: 10 July 2019
DOI: 10.1002/chir.23128
Revised: 6 August 2019
Accepted: 7 August 2019
S P E C I A L I S S U E A R T I C L E
Synthesis of alternating metallocopolymers by chiral
recognition
Maria Torres‐Werlé | Benoît Heinrich
Stéphane Bellemin‐Laponnaz
| Aline Maisse‐François |
Institut de Physique et Chimie de
Abstract
Strasbourg, CNRS—Université de
We report the synthesis of chiral enantiopure polytopic bridging ligands, which
may lead to the formation of metallosupramolecular polymers with zinc (II) as
metal linker. We show that chiral C2‐symmetric bisoxazoline ligands are useful
moieties to efficiently generate heterochiral complexes and thus polymeric
entities. The corresponding metallopolymers were further characterized by
powder X‐ray diffraction (PXRD) to obtain information on the level of crystal-
linity of our different metallopolymers.
Strasbourg, Strasbourg cedex, France
Correspondence
Stéphane Bellemin‐Laponnaz, Institut de
Physique et Chimie de Strasbourg,
CNRS—Université de Strasbourg, 23 rue
du Loess, Strasbourg cedex 67034, France.
Email: bellemin@unistra.fr
Funding information
French National Research Agency (ANR),
Grant/Award Number: ANR‐11‐LABX‐
0058_NIE
KEYWORDS
chiral bisoxazoline, metallopolymer, polytopic ligand, zinc
1 | INTRODUCTION
coordination under chirality control at the metal center,
which contains freely exchangeable ligands under ther-
Metallosupramolecular polymers that combine metal ions
and polytopic ligands enable constructing unprecedented
materials with specific properties and functions that are
of interest for fundamental research but also for the devel-
opment of new technologies.1,2 Indeed, the combination of
metal ions with polytopic—organic—ligands necessarily
imports the properties of the two components (organic
and inorganic) into the final polymer as well as additional
properties generated by the metal‐ligand coordination
such as luminescence. These metallopolymers are
obtained in a straightforward manner by a process of self‐
assembly of metal ions with a monomer having linked
units (ie, polytopic ligands), and the resulting polymer
may exhibit reversible polymerization/depolymerization
characteristics due to the strength of the coordinate inter-
actions.3-7
modynamic control.
We used the complementarity of these bisoxazoline
ligands to generate here alternating metallocopolymers.
Therefore, ditopic, tritopic, and tetratopic chiral ligands
have been synthesized for that purpose and then
used to generate metallopolymers. In all cases, the
metallopolymers were instantaneously formed upon addi-
tion of zinc salt to a mixture of two ligands of opposite
configuration. The resulting solids were characterized
including powder X‐ray diffraction studies.
2 | MATERIALS AND METHODS
2.1 | Chemicals and instruments
We have recently shown that while most of these poly-
mers consist of a single binding motif, it may be possible
to generate alternating metallopolymers with, for exam-
ple, two different ligands by means of a chiral molecular
instruction.8-10 The well‐defined construction of such
copolymers has been possible through heteroleptic
All manipulations were performed under an inert atmo-
sphere of argon or nitrogen using standard Schlenk line
techniques. Valinol was obtained by reduction of valine11;
1,1‐bis[(4S)‐4‐isopropyl‐4,5‐dihydrooxazol‐2‐yl]ethane (1)
was synthesized according to previous report.12,13 Sol-
vents were purified and degassed by standard procedures.
Chirality. 2019;1–7.
wileyonlinelibrary.com/journal/chir
© 2019 Wiley Periodicals, Inc.
1

2
TORRES‐WERLÉ ET AL.
All other reagents were commercially available and used
as received. Metallopolymers were obtained using metha-
(–NCH), 70.1, 69.8 (–OCH2), 43.3 (–CCH3), 41.8 (–CH2),
32.5, 32.2 (–CH (CH3)2), 21.2 (–C (CH3), 18.8, 18.7, 17.9,
17.5 (–CH (CH3)2); IR (KBr): ṽ = 1658 cm−1 (s, C═N); MS
(ESI +): m/z: 607.42 [M + H]+; elemental analysis calcd
(%) for C36H54N4O4: C 71.25, H 8.97, N 9.23; found C
70.97, H 8.89, N 9.21. (R)‐iPr‐DiBox was obtained using
the same procedure from 1,1′‐bis[(4R)‐4,5‐dihydro‐4‐
isopropyloxazol‐2‐yl]ethane.
1
nol as solvent (ACS reagent grade). H and 13C nuclear
magnetic resonance (NMR) spectra were recorded on a
Bruker AVANCE 300 spectrometer using the residual sol-
vent peak as reference (CDCl3: δH = 7.26 ppm; δC = 77.16
ppm) at 298 K. Chemical shifts are given in ppm (δ)
compared with TMS (tetramethylsilane). Infrared (IR)
spectra were recorded on a Nicolet 380 FT‐IR spectrome-
ter. KBr discs were made for all samples. Elemental
analyses were recorded by the “Institut de Chimie” labo-
ratory, Université de Strasbourg. HRMS ESI analyses
were recorded on microTOF, Bruker Daltonics by the
“Institut de Chimie” laboratory, Université de Strasbourg.
Specific rotations were recorded at the “Laboratoire de
Stéréochimie,” ECPM, Strasbourg. The XRD patterns
were obtained with a linear monochromatic Cu‐Kα1
beam (λ = 1.5405 Å) by using a sealed‐tube generator
(600 W) equipped with a bent quartz monochromator
and recorded with a curved Inel CPS120 counter gas‐
filled detector linked to a data acquisition computer. Peri-
odicities up to 70 Å can be measured, and the sample
temperature controlled to within 0.01°C from 20°C to
200°C. In all cases, the crude powder was filled in
Lindemann capillaries of 1‐mm diameter and 10‐μm wall
thickness.
2.2.2 | (S)‐iPr‐BP‐DiBox (3)
The general procedure was followed: 2.00 mmol (51%
yield). [α]D25: −0.59. 1H NMR (300 MHz, CDCl3): δ
(ppm) = 7.42 (d, J = 8.2 Hz, 4H; Harom), 7.21 (d, J = 8.3
Hz, 4H; Harom), 4.30‐4.23 (m, 4H; –NCH), 4.07‐3.91 (m,
8H; –OCH2), 3.33 (q, J = 13.5 Hz, 4H; –CH2), 1.85‐1.73
(m, 4H; –CH (CH3)2), 1.47 (s, 6H; –C (CH3), 0.95‐0.81
(m, 24H; –CH (CH3)2; 13C{1H} NMR (300 MHz, CDCl3):
δ (ppm) = 167.5 (N═CO), 139.5 (–Carom), 135.6 (–Carom),
130.8 (–Carom), 126.6 (–Carom), 72.0, 71.6 (–NCH), 70.1,
69.8 (–OCH2), 43.4 (–CCH3), 41.8 (–CH2), 32.4, 32.3
(–CH (CH3)2), 21.3 (–C (CH3), 18.8, 18.7, 17.9, 17.5
(–CH (CH3)2); IR (KBr): ṽ = 1655 cm−1 (s, C═N); MS
(ESI +): m/z (%): 684.45 [M + H]+; elemental analysis
calcd (%) for C42H58N4O4 (682.93): C 73.86, H 8.56, N
8.20; found C 73.94, H 8.60, N 8.02. (R)‐iPr‐BP‐DiBox
was obtained using the same procedure starting from
1,1′‐bis[(4R)‐4,5‐dihydro‐4‐isopropyloxazol‐2‐yl]ethane.
2.2 | Synthesis of polytopic bisoxazolines
2.2.3 | (S)‐iPr‐TriBox (4)
2.2.1 | (S)‐iPr‐DiBox (2): General
procedure14
The general procedure was followed to give the product
with identical analytical data as already reported by us.14
Dissolved in dry tetrahydrofuran (25 mL) was 1,1′‐bis[(4S)‐
4,5‐dihydro‐4‐isopropyloxazol‐2‐yl]ethane (1, 3.96 mmol,
1 g). A solution of 1.6 M nBuLi in hexane (4.31 mmol, 2.7
mL) was added dropwise at −78°C. After stirring for 15
minutes, the bath was removed, and α,α′‐dibromo‐p‐
xylene (1.96 mmol, 518 mg) was added. The mixture was
then stirred at room temperature for 12 hours. The
resulting mixture was washed with a saturated NH4Cl
solution, and the aqueous phase was extracted with dichlo-
romethane. The combined organic phases were dried over
Na2SO4. Evaporation of the solvent gave a colorless oil,
which was purified by silica gel column chromatography
(AcOEt/MeOH, 95/5) yielding a colorless viscous oil (1.56
2.2.4 | (S)‐iPr‐TetraBox (5)
The general procedure was followed to give the product
with identical analytical data as already reported by us.14
2.3 | Synthesis of metallopolymers
2.3.1 | Metallopolymer (6) [Zn + (R)‐iPr‐
DiBox + (S)‐iPr‐DiBox]: General procedure
1
mmol, 948 mg, 80%). [α]D25: −0.81 (c 0.5, CHCl3). H
Ligands (R)‐(2) (R)‐iPr‐DiBox and (S)‐(2) (S)‐iPr‐DiBox
(0.12 mmol, 75 mg each) were dissolved in methanol
(1.0 mL). The resulting colorless solution was stirred for
10 minutes before adding dropwise solution of Zn
(BF4)2 (0.24 mmol, 57 mg) in methanol (1.0 mL). The
mixture led to the instantaneous formation of an opaque
gel. The polymer was then isolated by addition of diethyl
NMR (300 MHz, CDCl3): δ (ppm) = 7.03 (s, 4H; Harom),
3
3
4.22 (dt, J = 8.0 Hz, J = 1.3 Hz, 4H; –NCH), 4.05‐3.90
(m, 8H; –OCH2), 3.24 (s, 4H; –CH2), 1.84‐1.67 (m, 4H;
–CH (CH3)2), 1.40 (s, 6H; –C (CH3), 0.94‐0.80 (m, 24H;
–CH (CH3)2; 13C{1H} NMR (300 MHz, CDCl3): δ (ppm) =
167.6 (N═CO), 134.9 (–Carom), 130.1 (–Carom), 72.0, 71.6

TORRES‐WERLÉ ET AL.
3
ether followed by filtration, giving a white powder in
quantitative yield. IR (KBr): ṽ = 1634 cm−1 (s, C═N); ele-
mental analysis calcd (%) for C72H108B4F16N8O8Zn2: C
51.12, H 6.43, N 6.62; found C 51.53, H 6.68, N 6.75. Since
the product is insoluble in most common solvents, the
NMR spectrum could not be taken. Thermogravimetric
analysis (TGA) revealed that the decomposition of the
samples occurs above 200°C, without crossing any phase
transition.
2.3.4 | Metallopolymer (9) [Zn + (R)‐iPr‐
DiBox + (S)‐iPr‐TriBox]
The general procedure was followed (0.25 mmol of Zn,
quantitative yield). 1H NMR (300 MHz, CD3OD): δ (ppm)
= 7.14‐6.99 (m, 7H, Harom), 4.40‐3.35 (m, 30H), 2.98‐2.92
(m, 10H), 1.96‐1.29 (m, 25H), 0.93‐0.85 (m, 60H). Elemen-
tal analysis calcd (%) for C210H318B12F48N24O24Zn6: C
50.48, H 6.41, N 6.73; found C 50.84, H 6.88, N 6.62.
2.3.5 | Metallopolymer (10) [Zn + (R)‐iPr‐
DiBox + (S)‐iPr‐TetraBox]
2.3.2 | Metallopolymer (7) [Zn + (S)‐iPr‐
BP‐DiBox + (R)‐iPr‐BP‐DiBox]
The general procedure was followed (0.25 mmol of Zn,
quantitative yield). 1H NMR (300 MHz, CD3OD): δ =
7.13‐6.99 (m, 6H, Harom), 4.87‐3.54 (m, 36H), 2.98‐2.92
(m, 10H), 1.98‐1.24 (m, 30H), 0.96‐0.85 (m, 72H). Elemen-
tal analysis calcd (%) for C138H210B8F32N16O16Zn4: C
50.15, H 6.40, N 6.78; found C 50.85, H 6.79, N 6.63.
The general procedure was followed (0.25 mmol of Zn,
quantitative yield). Since the product is insoluble in most
common solvents, the NMR spectrum could not be taken.
Elemental analysis calcd (%) for C84H116B4F16N8O8Zn2: C
54.72, H 6.34, N 6.06; found C 54.29, H 6.43, N 5.87.
3 | RESULTS AND DISCUSSION
2.3.3 | Metallopolymer (8) [Zn + (S)‐iPr‐
DiBox + (R)‐iPr‐BP‐DiBox]
The chiral ligands were synthesized according to the gen-
eral scheme described in Figure 1. They were obtained in
one step from methyl‐bis (oxazolinyl)methane derivative15
by deprotonation with n‐BuLi followed by reaction with
the appropriate electrophile (ie, α,α′‐dibromo‐p‐xylene,
α,α′‐dibromo‐p,p′‐bitolyl, 1,3,5‐tris (bromomethyl)‐ben-
zene or 1,2,4,5‐tetrakis (bromomethyl)‐benzene).16,17 All
compounds were characterized by classical analytical
The general procedure was followed (0.25 mmol of Zn,
quantitative yield). 1H NMR (300 MHz, CD3OD): δ
(ppm) = 7.51 (d, Jortho = 8.2 Hz, 4H; Harom), 7.25 (d, Jortho
= 7.9 Hz, 4H; Harom) 7.10 (bs, 4H, Harom), 4.39‐3.94 (m,
24H), 1.86‐1.71 (m, 20H), 0.94‐0.85 (m, 48H). Elemental
analysis calcd (%) for C78H112B4F16N8O8Zn2: C 52.48, H
6.41, N 6.30; found C 52.06, H 6.73, N 6.29.
FIGURE 1 Synthesis of polytopic
ligands in enantiomeric form from (S)‐(1)
or (R)‐(1). Conditions: (1) n‐BuLi, −78°C,
15 min in THF; (2) Electrophile (0.5, 0.33
or 0.25 equiv.), R.T. 12 h

4
TORRES‐WERLÉ ET AL.
methods. For the purpose of our studies, both enantiomers
of ditopic ligand (2) and (3) were synthesized whereas
ligand (4) and (5) were synthesized starting from (S)
valinol.
addition of diethylether and elemental analyses con-
firmed the purity of the products. Interestingly, all
attempts to generate metallopolymers using ligands with
the same absolute configuration were unsuccessful, thus
confirming the need of heterocomplementarity to form
the metal complexes. Figure 4 displays the methanol
solution containing equimolar amount of ligand (R)‐(2)
and (S)‐(3) prior to addition to the metal salt (A) and after
addition (B) showing the formation of the polymer (8).
On the basis of chiral molecular assemblies, the suc-
cessful construction of an alternate metallocopolymer is
only possible by formation of heterochiral complexes,
which has been shown to be possible using C2‐symmetric
bisoxazoline ligands. Indeed, the least sterically hindered
[ML2]‐type complex in a tetrahedral environment com-
bines two chiral C2‐symmetric bisoxazoline ligands of
opposite sign, as displayed in Figure 2.8,9 This strategy
allowed us to construct several metallopolymers with
ditopic ligands. We then decided to extend this strategy
to synthesize various metallopolymers in particular using
units with higher topicity.
Using ligands (2) to (5), we synthesized five different
zinc‐based metallopolymers as shown in Figure 3. In all
cases, they were instantaneously formed upon addition
of Zn (BF4)2 to a methanol solution containing two
ligands of opposite configuration and in the appropriate
stoichiometric proportion. Metallopolymers (6) and
(7) were generated from the racemic iPr‐DiBox
ligand (2) and iPr‐BP‐DiBox ligand (3), respectively.
Metallopolymer (8) was obtained from the iPr‐DiBox
ligand (R)‐(2) and iPr‐BP‐DiBox ligand (S)‐(3), whereas
metallopolymers (9) and (10) were obtained by combina-
tion of (R)‐(2) with the tritopic ligand (S)‐(4) or the
tetratopic ligand (S)‐(5), respectively. In all cases, a white
gel‐like material was spontaneously formed upon addi-
tion of the zinc precursor. All polymers have then been
isolated as white solids in close‐to‐quantitative yield by
1
Figure 4C displays the H NMR spectra of the resulting
polymer that has been isolated by precipitation with
diethylether and filtration. Integration of the signals con-
firmed the stoichiometric composition of resulting
metallopolymer.
We then studied our Zn (II) compounds by PXRD, to
obtain information on the level of crystallinity of our dif-
ferent products. In the case of the metallopolymer (6), the
structure turned out to be semicrystalline with
nanometer‐size crystals leading to broadened reflections,
as displayed in Figure 5.
Although the overlapping and the poorly defined posi-
tions of the reflections precludes the resolution of the
average crystalline structure, the information from PXRD
pattern is sufficient for a general description of the mate-
rial state. Specifically, the main diffracted intensity shares
in two groups of unresolved reflections: one at small
angles (around the major peak at 9.5° corresponding to
9.3 Å) from the lateral arrangement of polymer chains
and counterions, and a group at wide‐angles (18‐25° cor-
responding to 5‐3.5 Å) from periodicities in the range of
lateral distances between close‐packed molecular seg-
ments. Outside these groups, diffracted signals are
FIGURE 2 Shaping coordination spheres with chiral C2‐symmetric bisoxazoline derivatives: favorable combination in [Zn (bisox)2]2+
complexes in a tetrahedral environment, demonstrating the complementarity of opposite enantiomers

TORRES‐WERLÉ ET AL.
5
FIGURE 3 Synthesis of
metallopolymers 6‐10, using ditopic,
tritopic or tetratopic ligands (2‐5).
Conditions: MeOH at room temperature
FIGURE 4 Pictures of the resulting solution before (A) and after (B) complexation of Zn (BF4)2 with an equimolar amount of (R)‐(2) and
1
(S)‐(3); (C) H NMR spectra (CD3OD, aromatic region) of (S)‐iPr‐DiBox (top), (R)‐iPr‐BP‐DiBox (middle) and the corresponding copolymer
(bottom) obtained from Zn (BF4)2
essentially blurred out by the structural disorder, where-
upon the molecular organization could be considered as
“soft‐crystalline,” as meaning in a state intermediate
between crystalline and amorphous solids. For
metallopolymer (8), also shown in Figure 5, crystallinity
even totally vanished since the patterns only contains
two broad scattering signals from average lateral dis-
tances between polymer chains and molecular segments.
The similarity of their shapes and positions with those
of the unresolved reflection groups of (6) strongly sug-
gests close local‐range arrangements for both polymers.
They indeed contain the same metal ion and counterions,
whose arrangement into ionic strata drives the self‐
assembly. The nature of the organic spacers and their
sequence in the backbones allows however to modulate
the emerging structure or here to obtain such a structure
only for (6). The reason is obviously that (6) exclusively
associates enantiomeric units of type (2), while (8) alter-
nates type (2) and type (3) units: Complexes from succes-
sive strata are hence connected by a phenyl spacer in (6),
while they are either connected by a phenyl or a longer
biphenyl spacer in (8). Prerequisite for crystallization in
this latter case is that polymers self‐assemble in a way
that all spacers of same nature locate on the same side
of ionic strata. Such an unlikely configuration is perhaps
not possible for (8), which would then explain that this
polymer stays in an amorphous‐like state. Confirmation
of this view is brought by polymer (7) in Figure 5, for

6
TORRES‐WERLÉ ET AL.
perturb the close packing, and effectively, crystallinity
vanished for both copolymers. The patterns of these
amorphous‐like polymers display the two scattering sig-
nals from the local‐range close packing of entire polymers
and molecular segments. The shapes and positions of
these signals stay similar to those of the unresolved reflec-
tion groups of the linear polymer (6), indicating that ram-
ifications have little impact on the local‐range packing of
complexes and counterions.
4 | CONCLUSION
In conclusion, we have shown that using zinc ions alter-
nate metallocopolymers may be easily produced through
the formation of heterochiral [ML2]‐type complexes.
Indeed, chiral C2‐symmetric bisoxazoline derivatives
exhibit the good spatial arrangement to generate these
heterochiral species. When ditopic ligands of opposite
configuration were used such as (S)‐(2) and (R)‐(2) or
(S)‐(3) and (R)‐(3), semicrystalline solids were obtained.
Other combination led to amorphous solids, such as
pairing of (S)‐(2) with (R)‐(3). In addition, ligands of
higher topicity also led to amorphous materials. Indeed,
ramifications may perturb the close packing, and crystal-
linity disappears as soon as topicity of the ligand is higher
than 2. From these experiments, we can further conclude
that prerequisite for crystallization of linear
metallopolymers from ditopic ligands is that they self‐
assemble in a way that all spacers of the same nature
locate on the same side of the ionic strata.
FIGURE 5 PXRD patterns of metallopolymers (6) (bottom,
black), (8) (middle, red), and (7) (top, blue)
which both (2) units were replaced by (3), and thus all
phenyl spacers by biphenyl. Constrain from spacer loca-
tion was therefore removed and crystallization effectively
reappeared. Ionic parts being identical for (6) and (7),
structures are also quite similar, with in particular the
same major periodicity at 9.3 Å from the lateral arrange-
ment of polymers. There is nevertheless a striking differ-
ence in the regularity and correlation length of the
structures: For (7), reflections are substantially sharper
and appear in the whole scattering range; this material
is hence in a fine‐powdered crystalline state. It is unclear
why the spacer nature has this effect: Tentatively, it could
be related to the contribution of biphenyl to close packing
or to the higher spacing of ionic strata. Apart from mod-
ulating the emerging structure, the organic spacer offers
an easy route toward higher topicity and up to four coor-
dinating sites could be introduced on phenyl and com-
bined to ditopic ligands, to yield the metallocopolymers
(9) and (10), whose PXRD patterns are displayed in
Figure 6. It was expected that ramifications would
ACKNOWLEDGEMENTS
This work was funded by the French National Research
Agency (ANR) through the Programme d'Investissement
d'Avenir under contract ANR‐11‐LABX‐0058_NIE within
the Investissement d'Avenir program ANR‐10‐IDEX‐
0002‐02.
ORCID
Benoît Heinrich https://orcid.org/0000-0001-6795-2733
Stéphane Bellemin‐Laponnaz https://orcid.org/0000-0001-
9462-5703
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chiral recognition. Chirality. 2019;1–7. https://doi.
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