Amino acid derivatives of perylenediimide and their N-H...O peptide bond dipoles-templated solid state assembly into stacks

Article abstract of DOI:10.1039/c1ob06213a

A methodology is proposed to provide direct access in good yields to peptide residues-appended perylenediimides PDI-(Cl₄)-[Gly-Ala(OEt)] ₂, 2a, PDI-(Cl₄)-[Gly-Val(OEt)]₂, 2b and PDI-(Cl₄)-[Gly-Gly(OEt

Full text of DOI:10.1039/c1ob06213a

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PAPER
Amino acid derivatives of perylenediimide and their N–H ◊ ◊ ◊ O peptide bond
dipoles-templated solid state assembly into stacks†
Cyprien Lemouchi,a Sergey Simonov,a,b Leokadiya Zorina,a,b Christelle Gautier,a Pie´trick Hudhommea and
Patrick Batail*a
Received 20th July 2011, Accepted 1st September 2011
DOI: 10.1039/c1ob06213a
A methodology is proposed to provide direct access in good yields to peptide residues-appended
perylenediimides PDI-(Cl4)-[Gly-Ala(OEt)]2, 2a, PDI-(Cl4)-[Gly-Val(OEt)]2, 2b and
PDI-(Cl4)-[Gly-Gly(OEt)]2, 2c from a generic perylenediimide (PDI) platform symmetrically
functionalized with carboxylic acids at the imide sites, PDI-(Cl4)-[Gly(OH)]2, 1. The latter is obtained
in good purity by a non classical two-steps route avoiding the many, notoriously cumbersome
successive chromatography steps typical of PDI chemistry, and including a single final purification
allowing to crystallize the water soluble pure diacid 1, of great interest in its own right for further
developments in a variety of fields. Then, the synthesis, crystallization and analysis of the crystal
structures of 2a and 2b reveal a common pattern of self-assembly of the outer peptide residues based on
collections of parallel N–H ◊ ◊ ◊ O peptidic hydrogen bonds running alongside stacks where the
constraints imposed upon on the inner PDI skeletons by long range interaction of these parallel electric
dipoles reduce the dihedral angles around the bay regions by as much as 11% down to 32◦.
Introduction
The research reported here was designed as a materials-discovery
initiative to explore the outcome of competing intermolecular
hydrogen-bonding interactions1,2 in directing the structure of crys-
talline solids based on tetrachloro bay-substituted perylenediimide
(PDI-(Cl4)) cores3,4 whose both imide termini are functional-
ized by peptide residues,5,6 like PDI-(Cl4)-[Gly-Ala(OEt)]2, 2a,
PDI-(Cl4)-[Gly-Val(OEt)]2, 2b and PDI-(Cl4)-[Gly-Gly(OEt)]2, 2c
(Scheme 1). This objective requires the synthesis of PDI-(Cl4)-
[Gly(OH)]2, 1, a dicarboxylic acid PDI of interest in its own
right because of its expected solubility in water.6a,7 Our goal
was to devise a system whereby the pattern of overlap within
stacks of halogen-substituted, twisted p-conjugated skeletons with
enhanced electron acceptor ability4 would be modulated as a
Scheme 1
result of the demand of the hydrogen bond donor/acceptor
character of the outer peptide fragments. Our idea was that the
structure-directing ability of peptide residues8 would stabilize9
long range ordered electric dipole interactions within large col-
lections of intermolecular N–H ◊ ◊ ◊ O peptidic bonds and template
the formation of stacks, modulate the electrostatics of their
environment, and, ultimately, the charge carriers mobility.9,10
Although the importance of electrostatic interactions in biology
is intensely investigated,11 for example in the context of the role of
the environment on electron transfer in tetraheme cytochrome
c where the chemical activity of a heme propionate becomes
paramount,11a,b a recent trend has emerged where their significance
in tetrathiafulvalene-based materials chemistry and physics is ex-
plored with an emphasis on hydrogen bonded constructs.2,12,13 This
approach, extended herein to peptide-substituted PDIs, is inspired
by seminal work by Wu¨rthner and co-workers3,4,14–17 demonstrat-
ing the use of perylene-3,4,9,10-tetracarboxylic diimide derivatives
aLaboratoire MOLTECH-Anjou, CNRS, University of Angers, 49045,
Angers, France. E-mail: patrick.batail@univ-angers.fr
bInstitute of Solid State Physics, Russian Academy of Sciences, 142432,
Chernogolovka, MD, Russia
† Electronic supplementary information (ESI) available: UV-visible ab-
sorption spectra for 2a–c; Cyclic voltammograms (CV) of compounds
2a and 2b and CV of 1; Overlap modes for PDI-(Cl4)-[C2H4OH][4-
(n-C5H11)], PDI-(Cl4)-[4-(n-C12H25)C6H4], 2a and 2b. CCDC reference
numbers 833909 and 833910. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c1ob06213a
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as fluorophores for the construction of functional supramolecular
architectures self assembled by metal coordination or by hydrogen
bonding interactions into J-aggregates or gels. In that context, the
series of compounds 2 reported here are seen as novel precursors
of n-type semiconductors with potential prospects for applications
in photovoltaic devices, organic field-effect transistors and light-
emitting diodes.18 In that respect, a significant templating effect
by long range intermolecular N–H ◊ ◊ ◊ O peptidic bond dipoles
interactions is shown here to affect the structure of the twisted
PDI-(Cl4) skeletons and stacks topology.
Results and discussion
The synthesis of a PDI dicarboxylic acid such as 1 is challenging
because of several anticipated adverse factors like a lack of
solubility, the presence of polar acid carboxylic functions, and
a tendency to aggregate even at low concentrations. To prevent
aggregation and enhance solubility, a proven strategy is to
substitute the bay region by halides (Cl, Br) or amines, thereby
imposing a torsion angle of about 36◦ to the perylene core.3,4,19 The
tetrachloro-substituted PDI platform was also chosen to avoid
conformational isomerism imposed by different orientations of
tetraaryloxy substituents.
Scheme 2
washings only, that is, preventing the use of chromatography steps
notoriously cumbersome in PDI chemistry. Note that the success
of the methodology is the solubility of PDI-(Cl4)-[Gly(OH)]2, 1
in potassium carbonate aqueous solutions. Having reached that
level of purity for 1, independently of a further final purification
step discussed below, the compound was engaged in a peptide
coupling reaction (Scheme 1) following literature procedures5,8 to
yield 2a (57% yield) and 2b (54% yield) as red powdered materials
after purification by silica gel column chromatography. Finally,
a single chromatography on silica gel completes the compound
purification and delivers 1 in 65% yield with a good purity. 1
The synthesis of 1 typically involves a condensation reaction
between 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic di-
anhydride and an aliphatic amine carrying a protected carboxylic
function, here an amino acid H2N–CHR–CO2H. PDI-(Cl4)-
[Gly-OH]2, 1 (R = H) was our prime target since bulkier R
substituents have an adverse effect on crystallization20 and favor
the stabilization of liquid crystalline states instead.6d In order
to overcome the lack of solubility of any organic carboxylic
acid a common practice is to protect the latter as soluble
alkyl ester or benzyl ester derivatives that may be purified by
chromatography. Subsequent deprotection under acid or basic
conditions, like TFA, HBr/AcOH for tert-butyl ester or benzyl
ester, or an alkali hydroxide (LiOH, KOH, NaOH) for ethyl ester,
is well known to deliver diacid derivatives with a good purity.
However, PDI-(Cl4) cores remain sensitive to basic conditions
and nucleophilic attacks at the bay region. Therefore, cleavage
of the protecting group must take place under softer conditions,
preventing the use of nucleophilic bases. With these prerequisites
in mind, we synthesized PDI-(Cl4)-[Gly(OEt)]2, 3 and PDI-(Cl4)-
[Gly(OBzl)]2, 4 by condensing H-Gly-OEt and H-Gly-OBzl21
onto 1,6,7,12-tetrachloroperylene tetracarboxylic dianhydride22 in
good yields (Scheme 2). As anticipated, a complete deprotection
of the ethyl ester required an excess of LiOH yielding in turn
several by-products revealed on TLC-plates which could result
from a decomposition of the PDI-(Cl4)-core. Likewise, cleavage
of the benzyl ester with HBr/AcOH23 cannot be completed
under soft conditions and higher acid concentrations resulted
in side-reactions on the PDI-(Cl4)-core. Therefore, as exempli-
fied in Scheme 1, the reaction was carried out using 1,6,7,12-
tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride and the
unprotected glycine in propionic acid at reflux for 48 h,24 via a
Nucleophilic Addition Ring-Opening Ring-Closing mechanism.
This synthesis successfully delivers PDI-(Cl4)-[Gly(OH)]2, 1 in
one step with the notable interest that this direct route meets
the challenge of providing a reasonably pure dicarboxylic acid
with the additional benefit of a desirable work up using successive
proved to be readily soluble in THF allowing for H and 13C
1
NMR characterization in THF-d8. Single crystals of 1 are obtained
by slow evaporation out of a THF solution; note, however, that
the latter rapidly change into a crystalline powder preventing the
determination of their structure by X-ray diffraction.
Slow diffusion of ether in dimethylformamide solutions9,25 of 2
affords needle-like single crystals of both compounds. Note that
although these crystalline needles do not age well as they bent
with time and their faces become opalescent, a drawback that
precluded investigations of their transport properties, we were
able to collect X-ray diffraction data and determine their crystal
structures discussed below.
The electronic spectra for 1 and 2a–b (Figure S1†) all show
the three PDI characteristic bands at 427, 486 and 520 nm. Two
reversible reduction waves were detected (Figures S2†) at -0.77
and -0.94 V and -0.79 and -0.97 V vs. Fc+/Fc for 2a and 2b,
respectively, corresponding to the formation of radical anions and
dianions with no evidence for a reversible oxidation process, as
expected for tetrahalogeno-substituted PDI derivatives.4
Despite different crystal systems and space groups, the crystal
structures of PDI-(Cl4)-[Gly-Ala(OEt)]2, 2a (Fig. S3a†) and PDI-
(Cl4)-[Gly-Val(OEt)]2, 2b (Fig. S3b†) are remarkably similar. In
both compounds, one identifies slabs of stacks of tetrachloro
perylene diimide cores, the latter running along a in the triclinic
and orthorhombic unit cells, respectively. Hence, the whole of the
structural analysis comes down to a careful examination of the
compared stack topologies shown in Fig. 1.
The salient, distinguishing feature of both solids is the identi-
fication of self-assembled strings of N–H ◊ ◊ ◊ O hydrogen bonds.
Here, their inherent electric dipoles26 adopt a common, parallel
orientation, cooperating to provide a robust template for the p-
conjugated PDI-(Cl4) cores within the stack. One feature stands
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Fig. 1 A similar balance of N–H ◊ ◊ ◊ O and Cl ◊ ◊ ◊ Cl interactions templates
the pattern of intermolecular overlap of the twisted PDI-(Cl4) skeletons
along the stacks in (a) 2a and (b) 2b. In both compounds the stacks consist
of alternating two independent molecules. 2a: N ◊ ◊ ◊ O distances26 are in
˚
the range 2.96(1)–3.03(1) A; intra and inter Cl ◊ ◊ ◊ Cl PDI-(Cl4) skeleton
˚
˚
distances are 2.945(3)–3.102(3) A and 3.631(3)–3.835(3) A, respectively. 2b:
N ◊ ◊ ◊ O distances in the infinite string on the left are 3.040(9) and 3.087(8)
˚
A; antiparallel N ◊ ◊ ◊ O distances in the dimeric units on the right are a short
2.827(8)26a and 3.281(8)26b A. Intra and inter Cl ◊ ◊ ◊ Cl PDI-(Cl4) skeleton
˚
˚
˚
distances are 2.973(2)–3.095(2) A and 3.467(2)–3.903(2) A, respectively.
out though and differentiates the templating patterns between 2a
and 2b (Fig. 1): while identical antiparallel strings of parallel N–
H ◊ ◊ ◊ O dipoles run on both sides of any stack in 2a (Fig. 1a),
one string of similar parallel N–H ◊ ◊ ◊ O dipoles runs on the left-
hand side of the stack in 2b (Fig. 1b) when successive dimers of
antiparallel N–H ◊ ◊ ◊ O dipoles are stabilized on its right hand side.
Further insight on the strength of the templating effect
exerted upon the stack topology and inner PDI-(Cl4) skeletons
configuration by the self-assembly of the outer peptides residues
is gained by comparing in Fig. 2 a set of two stack characteristics
for 2a and 2b, namely the angle a between the stacking axis
a and the PDI intramolecular N–N axis (note that the shift
normal to N–N is identical for all four compounds, as shown
in Figure S4†), and the dihedral angles q1 and q2, with those
for two other compounds, PDI-(Cl4)-[C2H4OH][4-(n-C5H11)]19
and PDI-(Cl4)-[4-(n-C12H25)C6H4]4 for which these characteristics
Fig.
2
Evolution of the angle
a
and dihedral angles q1 and
q2 (between carbon atoms marked with solid dots) from (a)
PDI-(Cl4)-[C2H4OH][4-(n-C5H11)]19 to (b) PDI-(Cl4)-[4-(n-C12H25)C6H4],4
to (c) PDI-(Cl4)-[Gly-Ala(OEt)]2, 2a where q1 are 32(2)◦ and 34(2)◦ and q2
are 30(2)◦ and 32(1)◦; and (d) PDI-(Cl4)-[Gly-Val(OEt)]2, 2b where q1 are
36(1) and 32(1)◦, q2 are 31(1) and 31(1)◦.
(Fig. 2a and 2b) are quite similar. A significant discontinuity
is registered as a and q for 2a (Fig. 2c)◦ and 2b (Fig. 2d),
whose averaged values are 53◦ A and 32 , changes by 20%
˚
and -11%, respectively, from the reference compounds,
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PDI-(Cl4)-[C2H4OH][4-(n-C5H11)]
and
PDI-(Cl4)-[4-(n-
Synthesis of PDI-(Cl4)-[Gly-Ala(OEt)]2, 2a
C12H25)C6H4] with softer templates. This illustrates a significant
increase of constraints qualifying a discontinuity in a series
where long range electrostatic stabilization of large collections
of parallel N–H ◊ ◊ ◊ O peptidic bond dipoles imposes a harder
templating effect upon the inner, p-conjugated PDI-(Cl4) cores
along the stacks.
EDCI (197 mg, 1.03 mmol) then (L)-H-Ala-OEt, HCl (158 mg,
1.03 mmol) were successively added to a THF (40 mL) and 1,4-
dioxane (10 mL) mixture containing 1 (300 mg, 0.47 mmol), DIEA
(0.6 mL) and HOBT (139 mg, 1.03 mmol). The reaction mixture
was stirred at room temperature for 48 h and TLC monitored
(eluent: CH2Cl2 + 10% AcOH). The reaction mixture was poured
into 100 mL of CH2Cl2; the solution was washed with aqueous
NaHCO3 and H2O. The organic layer was dried over MgSO4,
filtered and evaporated under reduced pressure. The red solid
residue was purified by column chromatography on silica gel using
a mixture 90/10 CH2Cl2/acetic acid solutions as the eluent. 2a is
obtained as a red solid (225 mg, 57%) and it was crystallized by
slow diffusion liq/liq. of Et2O in a solution of 2a dissolved in
DMF.
Conclusions
The aforementioned results demonstrate that the self-assembly of
outer peptide residues attached to PDI-(Cl4) skeletons is directed
by electrostatic stabilization of large collections of parallel N–
H ◊ ◊ ◊ O peptidic bond dipoles. A clear and distinctive influence,
and exquisite level of control, of the peptide residues over
two structural parameters, the lateral shift and curvature of
the PDI-cores along the stacks, is expressed in the angles a
and dihedral angles q, characteristic of a tandem-modal self-
assembly in the crystalline solid state. We are now applying the
synthetic methodology reported herein to the preparation of
novel series of peptidic PDIs with the objective to engage their
anionic carboxylate forms in conducting crystalline radical cation
salts;9,10 to tailor precursors of bulk, self-assembled crystalline
frameworks27 or molecular layers at metal surfaces;27a,c,e as well
as for applications in photovoltaic devices, organic field-effect
transistors and light-emitting diodes,3,4,14–18 where a modulation of
the electronic structure upon peptide-driven6 self-assembly need
to be investigated further.
◦
DSC: Tdec. = 312 C;1H NMR (CDCl3, 300 MHz) d 8.63 (4H,
s), 6.66 (2H, d, J = 7.5 Hz), 4.91 (4H, m), 4.63 (2H, q1d2, J1 = 7.5
Hz, J2 = 7.5 Hz), 4.23 (4H, q, J = 7.5 Hz), 1.47 (6H, d, J = 7.5 Hz),
1.29 (6H, t, J = 7.5 Hz);13C NMR (CDCl3, 300 MHz) d 172.9,
165.6, 162.0, 135.4, 133.2, 131.4, 128.8, 122.8, 61.7, 48.5, 42.9,
18.6, 14.1; MALDI-TOF (pos. mode) calcd for [C38H28Cl4N4O10]+:
840.1; found 840.1.
Synthesis of PDI-(Cl4)-[Gly-Val(OEt)]2, 2b
The synthetic procedure for 2a was applied using (L)-H-Val-OEt,
HCl. 2b is obtained as a red solid (227 mg, 54%); it is crystallized
by slow diffusi◦on liq/liq. of an Et2O solution of 2b in DMF. DSC:
1
Tdecomp. = 337 C; H NMR (CD2Cl2, 300 MHz) d 8.61 (s, 4H),
6.63 (d, 2H, J = 7.5 Hz), 4.90 (m, 4H), 4.56 (m, 2H), 4.22 (m, 4H),
2.19 (oct, 2H, J = 7 Hz), 1.29 (t, 6H, J = 7.5 Hz), 0.97 (t, 12H, J =
7 Hz); 13C NMR (CD2Cl2, 300 MHz) d 172.1, 166.6, 162.3, 135.7,
133.3, 131.8, 129.2, 123.8, 123.2, 61.8, 57.8, 43.3, 32.0, 19.1, 18.0,
14.4; MALDI-TOF (pos. mode) calcd for [C42H36Cl4N4O10 + H]+:
897.1; found 896.9. Anal. Calcd. for: C, 56.14; H, 4.04; N, 6.24.
Found: C, 55.65; H, 3.94; N, 6.24.
Experimental section
Synthesis of PDI-(Cl4)-[CH2-CO2H]2 or PDI-(Cl4)-[Gly(OH)]2, 1
Glycine (3 g, 40 mmol) was added to
a solution of
1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride
(BASF)22 (3 g, 5.68 mmol) in propionic acid (50 mL). The reaction
mixture was heated under reflux for 48h. After cooling, the
reaction mixture was poured into a 50 : 50 mixture of THF and
saturated NH4Cl aqueous solution. Following a first extraction,
the isolated red THF layer was poured into of saturated K2CO3
aqueous solution; gas evolved from the solution, the red-colored
water layer was extracted with THF (2 ¥ 50 mL). Then, 100 mL
of THF were added under stirring to the former and the mixture
was acidified upon adding dropwise a 6 N HCl solution to reach
a pH of 3, by which a red coloration of the organic layer and
a total discoloration of the water layer took place. The mixture
was then stirred for 20 min and extracted. The THF layer isolated
by extraction was evaporated to dryness under reduced pressure.
The red solid 1 was washed successively with water (2 ¥ 50 mL)
and Et2O (3 ¥ 50 mL) and dried overnight. The solid residue was
purified by column chromatography on silica gel using a 90/10
CH2Cl2/acetic acid mixture as eluent. A red powder (2.4 g, 65%)
Synthesis of PDI-(Cl4)-[Gly-Gly(OEt)]2, 2c
The synthetic procedure for 2a was applied using H-Gly-OEt, HCl.
2c is obtained as a red solid (233 mg, 61%). Tdecomp. = 300 ◦C. 1H
NMR (CD2Cl2, 300 MHz) d 8.68 (s, 4H), 6.36 (t, 2H, J = 7 Hz),
4.92 (s, 4H), 4.23 (q, 4H, J = 7 Hz), 4.07 (d, 4H, J = 7 Hz), 1.27
(t, 6H, J = 7 Hz); 13C NMR (CD2Cl2, 300 MHz) d 169.9, 166.
7, 162.5, 135.8, 133.4, 123.2, 62.0, 41.9, 30.1, 14.3; MALDI-TOF
(pos. mode) calcd for [C36H24Cl4N4O10 + H]+: 813.0; found 812.8.
Synthesis of PDI-(Cl4)-[CH2-CO2Et]2 or PDI-(Cl4)-[Gly(OEt)]2, 3
Glycine ethyl ester hydrochloride (578 mg, 4.16 mmol) was
added to a solution of 1,6,7,12-tetrachloroperylene-3,4,9,10-
tetracarboxylic dianhydride22 (1 g, 1.89 mmol) in toluene (50 mL).
The reaction mixture was heated under reflux for 24h. After
cooling, the reaction mixture was evaporated to dryness under
low pressure. The collected red solid was purified by silica gel
column chromatography with dichloromethane as eluent. A red
powder (1.1 g, 85%) was obtained. DSC: an exothermic peak at
290 ◦C signals a phase transition prior to the decomposition at
◦
1
was isolated. DSC: Tdec.: 267 C; H NMR (THF-d8, 300 MHz)
d 8.71 (s, 4H), 3.63 (s, 4H); the signal for the COOH proton
was too broad to be correctly described; 13C NMR (THF-d8,
300 MHz) d 169.6, 163.0, 136.5, 133.8, 133.1 130.2, 125.0, 42.4;
MALDI-Tof calcd for C28H10Cl4N2O8: 641.92; found 641.9. Anal.
Calcd. for: C, 52.20; H, 1.56; N, 4.35. Found: C, 51.64; H, 2.03;
N, 3.89.
◦
1
Tdec. = 312 C; H NMR (CD2Cl2, 300 MHz) d 8.7 (s, 4H), 4.94
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(s, 4H), 4.25 (q, 4H, J = 7.5 Hz), 1.31 (t, 6H, J = 7.5 Hz); 13C
NMR (CD2Cl2, 300 MHz) d 167.9, 162.3, 135.8, 133.4, 131.9,
129.4, 123.2, 62.2, 42.0, 14.4; MALDI-TOF (pos. mode) calcd for
[C32H18Cl4N2O8]+: 698; found 697.9.
3 (a) F. Wu¨rthner and M. Stolte, Chem. Commun., 2011, 47, 5109; (b) F.
Wu¨rthner, Chem. Commun., 2004, 1564.
4 Z. Chen, M. G. Debije, T. Debaerdemaeker, P. Osswald and F.
Wu¨rthner, ChemPhysChem, 2004, 5, 137.
5 R. Behrendt, M. Schenk, H-J. Musiol and L. Moroder, J. Pept. Sci.,
1999, 5, 519.
6 There is a current strong interest in the chemistry of perylene diimide-
carboxylics, especially of peptide carboxylic-substituted PBI’s: (a) F.
Yukruk, A. L. Dogan, H. Canpinar, D. Guc and E. U. Akkaya, Org.
Lett., 2005, 7, 2885; (b) O. Ozcan, F. Yukruk, E. U. Akkaya and D.
Uner, Appl. Catal., B, 2007, 71, 291; (c) E. Mete, D. Uner, M. Cakmak,
O. Gu¨lseren and S. Ellialtoglu, J. Phys. Chem. C, 2007, 111, 7539; (d) Y.
Xu, S. Leng, C. Xue, R. Sun, J. Pan, J. Ford and S. Jin, Angew. Chem.,
Int. Ed., 2007, 46, 3896; (e) D. Cakir, O. Gu¨lseren, E. Mete and S.
Ellialtioglu, J. Phys. Chem. C, 2011, 115, 9220.
7 (a) H. Y. Au-Yeung, P. Pengo, G. Dan Pantos, S. Otto and J. K. M.
Sanders, Chem. Commun., 2009, 419; (b) B. M. Bulheller, G. Dan
Pantos, J. K. M. Sanders and J. D. Hirst, Phys. Chem. Chem. Phys.,
2009, 11, 6017; (c) F. B. L. Cougnon, H. Y. Au-Yeung, G. Dan Pantos
and J. K. M. Sanders, J. Am. Chem. Soc., 2011, 133, 3198.
Synthesis of PDI-(Cl4)-[Gly(OBzl)]2, 4
4
was prepared from 1,6,7,12-tetrachloroperylene-3,4,9,10-
tetracarboxylic dianhydride22 (1 g, 1.89 mmol) and Glycine benzyl
ester trifluoroacetic salt21 ((1.2 g, 4.15 mmol) following the
procedure for 3. 4 is isolated as a red solid (1.3 g, 81%). DSC:
Tdec. = 322 ◦C; 1H NMR (CD2Cl2, 300 MHz) d 8.71 (s, 4H), 7.38
(m, 10H), 5.24 (s, 4H), 5.02 (s, 4H); 13C NMR (CD2Cl2, 300 MHz)
d 167.9, 162.3, 135.8, 133.5, 129.5, 129.0, 128.8, 128.5, 123.2, 67.8,
42.0; MALDI-TOF (pos. mode) calcd for [C42H22Cl4N2O8 + H]+:
823.0; found 823.0. Anal. Calcd. for: C, 61.19; H, 2.69; N, 3.40.
Found: C, 60.04; H, 2.83; N, 3.13.
8 Y. Li, G. Li, X. Wang, W. Li, Z. Su, Y. Zhang and Y. Ju, Chem.–Eur. J.,
2009, 15, 6399.
9 A. El-Ghayoury, C. Me´zie`re, S. Simonov, L. Zorina, M. Cobia´n, E.
Canadell, C. Rovira, B. Na´fra´di, B. Sipos, L. Forro´ and P. Batail,
Chem.–Eur. J., 2010, 16, 14051.
10 (a) L. Zorina, S. Simonov, C. Me´zie`re, E. Canadell, S. Suh, S. E. Brown,
P. Foury-Leylekian, P. Fertey, P. Pouget and P. Batail, J. Mater. Chem.,
2009, 19, 6980; (b) Y. Lakhdar, C. Me´zie`re, L. Zorina, M. Giffard,
P. Batail, E. Canadell, P. Auban-Senzier, C. Pasquier, D. Je´rome, B.
Na´fra´di and L. Fo´rro´, J. Mater. Chem., 2011, 21, 1516.
X-Ray structure analysis
2a: C38H28Cl4N4O10, M = 842.44, T = 150(1)K, triclinic, P1, a =
˚
9.978(3), b = 10.704(3), c = 17.817(6) A, a = 74.10(2), b = 81.31(2),
◦
g = 81.28(2) , V = 1796.9(9) A , Z = 2, Dc = 1.557 g cm-3,
3
˚
m = 3.97 cm-1, F(000) = 864, 2Hmax = 56.0◦, reflections measured
16721, unique reflections 11506 (Rint = 0.0668), reflections with
I > 2s(I) = 6817, parameters refined 885, R1 = 0.0713, wR2 =
0.1169, GOF = 1.015. 2b: C42H36Cl4N4O10, M = 898.55, T =
150(1)K, orthorhombic, P212121, a = 10.019(2), b = 16.372(3),
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3
-3
˚
˚
c = 49.573(9) A, V = 8132(3) A , Z = 8, Dc = 1.468 g cm ,
m = 3.56 cm-1, F(000) = 3712, 2Hmax = 52.1◦, reflections measured
44150, unique reflections 11623 (Rint = 0.0686), reflections with I >
2s(I) = 7584, parameters refined 1095, R1 = 0.0642, wR2 = 0.1241,
GOF = 1.036. Single crystal X-ray diffraction data were collected
at 150 K using a Bruker Nonius KappaCCD diffractometer with
˚
monochromatized Mo-Ka-radiation (l = 0.71073 A, graphite
monochromator, combined j/w-scans). Empirical absorption
correction of experimental intensities was applied using the
SADABS program.28 The structures were solved by a direct
method followed by Fourier syntheses and refined by a full-matrix
least-squares method using the SHELX-97 programs.29 All non-
hydrogen atoms were refined in an anisotropic approximation. H-
atoms were placed in idealized positions and refined using a riding
model, Uiso(H) = 1.2Ueq(C). CCDC 833909 and 833910 contain
the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crys-
tallographic Data Centre via www.ccdc.cam.ac.uk/data_request/
cif.
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