Light absorption and hole-transport properties of copper corroles: From aggregates to a liquid crystal mesophase

Article abstract of DOI:10.1039/c5nj01268f

The synthesis of the corrole-based liquid crystal phase CorLC is described together with its full characterization using a combination of Polarised Optical Microscopy (POM), ThermoGravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) measure

Full text of DOI:10.1039/c5nj01268f

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DOI: 10.1039/C5NJ01268F
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many research areas including catalysis,10 sensors11 or
medicine.12 Nevertheless, very few reports concern the
preparation and characterization of large corrole-based
+PVTQFWEVKQP
assemblies13 and their incorporation into electronic devices.14
We report here the synthesis and full characterization of a
copper corrole-based liquid crystal mesophase CorLC (Scheme
1). Its supramolecular organization was studied by UV/Visible
spectroscopy and was compared to the ones produced by
The highly versatile optical, electronic and photophysical
properties of porphyrin and phthalocyanine derivatives has led
to their large application in the fields of organic electronics and
optoelectronics.1 In this regard, their ability to produce large
assemblies or aggregates is particularly employed to construct
organized and high light-absorbing materials displaying
efficient charge and/or exciton transport properties that are
essential in the preparation of organic solar cells2 or
photoconductors.3 Among the different supramolecular tools
that are used to build self-organized porphyrin and
phthalocyanine systems, their incorporation in liquid crystal
(LC) phases4 is attractive since the morphology and orientation
of LC thin films can be controlled to obtain large area and
defect free devices.5 For example, an exciton diffusion length
longer than 12 nm has been measured in a nematically
organized porphyrin layer6 while a field-effect mobility of 0.7
cm2 V-1 s-1 was exhibited by an Organic Field Effect Transistor
aggregates of its parent meso triaryl (Cor1) and per-aryl (Cor2
)
derivatives (Scheme 1). The hole-transport properties of these
three compounds were additionally measured through their
incorporation in OFETs.
ꢀ
4GUWNVUꢀCPFꢀFKUEWUUKQPꢀ
Synthesis of the mesogen CorLC.
The liquid crystal CorLC was prepared in four synthetic steps
starting
methoxyphenyl)corrole Cor1 (Schemes 1 and S1, ESI†).15 The
full bromination of -positions followed by a Suzuki cross-
from
the
copper(III)
meso-tris(p-
E
coupling procedure afforded the per-aryl substituted copper
(OFET)
incorporating
a
liquid
crystalline
copper corrole Cor2 as previously reported.16 A demethylation using
standard conditions afforded the per-aryl complex substituted
by eleven p-hydroxyphenyl groups in 44% yield without any
Corrole and its metal complexes are currently
phthalocyanine.7
ꢀ
noticeable removal of the copper ion. It has to be noted that
this latter derivative is enough soluble in sufficiently polar
media in order to be purified and characterized. The expected
compound CorLC was prepared in a yield of 23% by the
subsequent condensation of an excess of the benzyl chloride
attractive members of the porphyrinoid family since their
syntheses8 and functionalizations9 have been extensively
developed during the last fifteen years and are thus amenable to
gram-scale synthesis, sometimes essential for developing
devices. Consequently, corrole derivatives are employed in
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀandꢀtheꢀCentreꢀNationalꢀdeꢀlaꢀRechercheꢀScientifiqueꢀ2013ꢀꢀ
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derivative
1 in basic conditions. Its purity was confirmed by its phase characterized by a fan texture that strongly suggests that
1H NMR spectrum and by its MALDI-TOF spectrum showing the compound self-organizes in a columnar hexagonal (Colh)
View Article Online
DOI: 10.1039/C5NJ01268F
only its molecular peaks and the corresponding sodium adduct liquid crystalline phase (Fig. 1a). This preliminary result was
(ESI†). We note here that if a reaction has to be performed confirmed by DSC (Fig. 1b). The solid complex CorLC was
more than tenfold on the same substrate, without allosteric transformed to the Colh mesophase through a broad first order
effects, it is remarkable that the overall yield is in the two digit transition (-30 °C,
ǻ ǻ
H = 80.4 kJ·mol-1, S = 330.5 J·mol-1·K-1)
region.
that preceded a second first order transition (103.4 °C,
ǻH =
22.1 kJ·mol-1, S = 58.8 J·mol-1·K-1) of the Colh phase into the
ǻ
liquid isotropic state I.
a)
b)
Cooling
Colh
I
G
Colh
G
Colh
Colh
I
Heating
Scheme 1 Synthesis of the liquid crystal corrole CorLC. i) a)
Br2, pyridine, CHCl3; b) NaS2O5, H2O (45%). ii) Pd2(dba)3,
c)
d10
d11 d20 d21
K2CO3,
p-H3CO-C6H4-B(OH)2, toluene (71%). iii) BBr3,
CH2Cl2 (44%). iv) K2CO3, DMF (23%).
Thermal behaviour of CorLC.ꢀꢀ
The thermal behavior of CorLC was studied by a combination
of Polarised Optical Microscopy (POM), ThermoGravimetric
Analysis (TGA), Differential Scanning Calorimetry (DSC)
measurements and Small-Angle X-Ray Diffraction (SA-XRD)
(Fig. 1, Fig. S1, S2 and S3, ESI†). The TGA measurement
indicates that the compound is stable up to 300 °C (Fig. S1,
ESI†). Temperature dependent POM observations showed a
fluid and birefringent texture that is typical of the occurrence of
a liquid-crystalline organization. This texture does not show
any significant changes until the isotropisation occuring at
103 °C i.e. a transition from the liquid crystalline phase to the
standard liquid state (I). Upon cooling, this phase transition is
reversible and occurs at 95 °C (i.e. with a small hysteresis).
Notably, the liquid crystal phase remains birefringent and fluid
at room temperature. Cooling down the isotropic liquid sample
at very low speed (0.1 °C·min-1) forms the liquid crystalline
hch
hCol
Fig. 1 (a) Optical texture observed by the POM of CorLC in
the Colh mesophase at 90 °C after cooling from the isotropic
liquid. (b) DSC trace of CorLC recorded at 5 °C/min (second
heating and cooling). (c) SA-XRD profile in the liquid
crystalline phase and associated indexation of CorLC at 30 °C.
Structure of the CorLC mesophase.ꢀꢀ
2ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1Ͳ3ꢀ
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Cor1
, Cor2 and CorLC (Fig. 2). The per-aryl substitution
Temperature-dependent SA-XRD patterns of CorLC were
recorded in the 20-140 °C temperature range. The presence of a
large and diffuse signal at approximately 4.5 Å (hch), which was
associated with the liquid-like molten chains confirmed the
fluid-like nature of the mesophase. Short acquisition times (i.e.
10 min per scan) allowed to detect a very weakly temperature-
dependent sharp and intense signal at low angle in the 20-100
°C temperature range. A longer acquisition time at 30 °C (i.e.
24 hours) revealed the presence of three additional very weak
reflections in the low angle region (Fig. 1c)). These four sharp
reflections were indexed as (hk) = (10), (11), (20), (21)
produces the broadening of the Soret band which is red-shifted
from 433 nm in the spectrum of Cor1 to 463 nm aVniedw4A6rt4iclenOmnliinne
DOI: 10.1039/C5NJ01268F
the respective electronic spectra of Cor2 and CorLC. On the
other side, the replacement of the methyl groups of Cor2 by
benzyl substituents in CorLC does not induce any significant
change in the location of the B and Q bands and on the shape of
the UV/visible spectrum. This similarity is due to the equivalent
electron-donating properties of these two groups and shows that
the concomitant introduction of 11 additional aryl groups and
21 peripheral alkyl chains does not produce any supplementary
distortion of the aromatic corrole ring.
(squared spacing ratios h2
+ + hk = 1, 3, 4, 7; see Fig. S2,
k2
Thin solid films of Cor1, Cor2 and CorLC were prepared
by the slow evaporation of their respective dichloromethane
solutions. The formation of aggregates is illustrated by the
broadening of the resulting electronic spectra that gives, in
addition, insights of the relationship between the corroles
substitutions and their supramolecular organizations (Fig. 2).
ESI†) confirming the formation of a Colh arrangement
suggested by the POM observation (plane group p6 or p6mm).17
A unit cell parameter of
S
a = 41.1 Å and a cross-sectional area of
= 1462 Å2 were thus deduced from this last measurement.
The pattern recorded at 30 °C shows a second broad reflection
(hCol) located at about 7 Å partially overlapping the first one
corresponding to the molten aliphatic chains (i.e. hch). The
separation of these two broad signals by fitting them with
Gaussian functions (Fig. S3, ESI†) allowed to accurately
determine the value of hCol = 6.86 Å. Making the assumption
that hCoh corresponds to the separation between the complexes
1
Cor1
within a column, we thus calculated a volume of
10029 Å3 for an hexagonal columnar unit cell. Taking into
account a realistic density of
= 1.0 g·cm-3 in the mesophase,17d
V = S·hCol =
d
we estimated that the number of complexes CorLC per unit
cell Z amounts to 1 according to equation (1) where Nav is the
Avogadro’s number, MMm is the molecular weight of the
0
molecule in g·mol-1, and
V is the volume of the unit cell in
350
350
350
450
450
450
550
650
750
750
750
Å3.17d The liquid crystalline supramolecular organization of
complex CorLC should thus be considered as a bidimensional
long-ranged network with a rather disorganized third direction
(i.e. along the column axis) that is typical of Colh organizations.
This kind of organization is commonly observed in mesophases
produced by porphyrin- and phthalocyanine-based discotic
derivatives bearing multiple long alkyl chains.4 For example, a
Colh organization was also displayed by a porphyrin bearing
four peripheral mesogenic bis-dodecyloxy aryl groups which
1
Cor2
are similar to those born by CorLC 4b
.
0
1
550
650
(1)ꢀܼ ൌ ሺ݀Ǥ ܰ Ǥ ܸǤ ͳͲିଶସሻ ൊ ܯܯ ൌ ͲǤͻͶ̱ͳꢀꢀ
஺௏
௠
CorLC
Aggregation properties of Cor1, Cor2 and CorLC.ꢀꢀ
Copper meso-triarylcorroles are known to show hyper
electronic spectra that are strongly sensitive to the nature of the
మ
మ
meso-substituents that are involved in phenyl-to-Cu(
݀
)
௫ ି௬
charge transfers and contribute to the main Soret band peak.18
This orbital interaction is due to and increases with the saddling
of the macrocycle which is reinforced by the introduction of
0
bulky E
-aryl groups.16,19 This effect is here illustrated by the
550
O (nm)
650
UV/Visible spectra of diluted dichloromethane solutions of
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a threshold voltage VT of +38.5 V and an on/off ratio of 10. All
devices incorporating CorLC failed to give charge-transport
Fig. 2 Normalized UV-Visible absorption of diluted
dichloromethane solutions (dashed lines) and thin solid films
(solid lines) of Cor1, Cor2 and CorLC.
View Article Online
properties. Identical results were obtained when an hydrophobic
substrate Si/SiO2 modified by
a
gDraOfIt:e1d0.10s3e9l/fC-5aNssJe0m126b8lyF
monolayer of long alkyl chains was used to induce the
homeotropic alignment of the CorLC discotic molecules.21
Although thin films were cast as such, or with an annealing
step, these failed to improve the microstructural order for
The band maxima are red-shifted by ca 15 nm when assemblies
of Cor1 are produced because of the probable formation of J-
aggregates. This supramolecular architecture is commonly
achieving more efficient charge transport properties in Cor1
,
observed in the single crystal X-ray structures of copper meso
-
Cor2 and CorLC thin films. However, these functional
transistors are the first examples of OFETs using corrole
derivatives as active layers and the variation of their low
efficiencies are still illustrating the impact of the peripheral
substitution on the corroles supramolecular organization.
triarylcorrole derivatives where corrole assemblies are formed
thanks to, among others, an intermolecular interaction between
the meso-aryl group of one complex with the metallic centre of
the adjacent one producing short inter-macrocycle distances.20
On the other side, the per-aryl substitution of Cor2 and CorLC
induces the formation of H-aggregates as evidenced by the ca
20 nm blue-shift of their Soret band maxima (Fig. 2). The
peripheral sterical hindrance of Cor2 combined with the
multiple intermolecular interactions between alkyl chains in the
LC phase CorLC, inhibits the direct participation of the copper
ion in the supramolecular organization and thereby allows the
formation of a different intermolecular packing. The formation
of H-assemblies along the column axis is in accordance with
the Colh organization of the CorLC mesophase (see below).
a)-2,5E-03
-100
-2,0E-03
-1,5E-03
-60
-1,0E-03
-5,0E-04
-10
0,0E+00
VG (V)
Hole-transport properties of Cor1 and Cor2.ꢀꢀ
5,0E-04
0
-20
-40
-60
-80
-100
To further study the physico-chemical properties of Cor1
,
VD (V)
Cor2 and CorLC assemblies, their charge-transport properties
were investigated through their incorporation in OFETs.
Bottom-gate thin-film transistors with bottom electrode
contacts were fabricated to realize so-called BGBC (Bottom-
Gate Bottom-Contact) devices. Linear channel lengths (L = 25
or 50 μm) were realized by vacuum evaporation of gold
through a shadow mask directly on the gate. To complete the
device structure, the depositions of the active layers were
achieved by drop-casting of dichloromethane solutions (or
liquid CorLC) onto the surface of linear BGBC devices. All
measurements were performed in air and at room temperature.
Even if numerous OFETs were prepared for each derivative,
only the two best results obtained among the operating
transistors are presented herein.
-10
b) 3,5E-03
0
2,5E-03
1,5E-03
5,0E-04
-5,0E-04
10
60
VG (V)
0
20
40
60
80
100
VD (V)
A field effect transistor activity was observed for Cor1 and
Cor2-based assemblies by applying a negative drain and
negative gate voltages in order to operate in the accumulation
mode. These results demonstrate that Cor1 and Cor2 behave as
p-type semiconductors in air as shown by the typical output
characteristics of a Cor1-based OFET on Si/SiO2 substrate
under negative and positive voltages (Fig. 3a and Fig. 3b).
Under negative gate voltages, the successive increase of the
drain current indicates that the BGBC device based on Cor1
operates as an accumulation mode p-channel device (Fig. 3a).
The transport of positive carriers is confirmed by the depletion
mode under positive voltages (Fig. 3b). In the depletion mode,
carriers are driven away from the semiconductor interface,
which leads to a decrease of the drain current. The field effect
Fig. 3 Output characteristics of an OFET incorporating Cor1
under a) negative and b) positive voltages.
Table 1: Field effect mobilities (ȝ), threshold voltages (VT) and on/off
ratio (Ion/Ioff) of corrole-based OTFT devices
.
μ (cm2.V-1.s-1)
VT (V)
Ion/Ioff
+14,8
+38,5
24,5
a10
Cor1
Cor2
1,36u10-6
1,32u10-7
mobility (ȝ), threshold voltage (VT) and on/off ratio (Ion/Ioff) of
%QPENWUKQPUꢀ
the most efficient OFETs incorporating Cor1 and Cor2 are
summarized in Table 1 (All results are presented in Table S1,
ESI†). The highest field effect mobility in the saturation regime
at VD = -90 V was extracted for Cor1 and gives a value of
We described herein the synthesis and full characterization of
the first example of a corrole-based liquid crystal mesophase
(CorLC). This mesophase features, at room temperature, an
1.36u
10-6 cm2/V.s-1 together with a threshold voltage VT of
hexagonal columnar organization combined with an H-
arrangement of the discotic chromophores producing a blue
shifted light absorption. This study shows that the introduction
of numerous peripheral groups on copper corroles tunes their
+14.8 V and an on/off ratio of 24.5. The increasing sterical
hindrance of the peripheral substitution of Cor2 probably
produces a lower mobility of 1.32u
10-7 cm2/V.s-1 together with
4ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1Ͳ3ꢀ
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aggregation modes and their hole-transport properties. Since the
copper ion can be removed using mild experimental
conditions,22 CorLC can be used to prepare liquid crystal
phases incorporating other metallic centers such as Co(III)11a
and Mn(III)14a that are already applied in the fields of sensors.
OFET preparations and studies
Cor1, Cor2 and CorLC were dissolved in CH2Cl2 to a concentration of ca
View Article Online
DOI: 10.1039/C5NJ01268F
5.10-3 M. The Bottom-Gate Bottom-Contact (BGBC) configuration was
used for the OTFT devices. Highly n-doped silicon wafers (gate), covered
with thermally grown silicon oxide SiO2 (3000 Å, insulator layer), were
purchased from Vegatec (France) and used as bottom-gate substrates.
The capacitance per unit area of silicon dioxide dielectric layers was
1.2u10-8 F/cm2. The gold (Au) source and drain electrodes (channel length
L = 25 or 50 Pm, channel width W = 1 mm) were evaporated directly on
SiO2 layer prior the organic deposition through a shadow mask. Solutions
of Cor1, Cor2 and CorLC (or pure liquid CorLC) were deposited by drop-
casting to form the organic active layers in OTFT devices through a
dropwise addition of 20-40 μL volumes onto the devices surfaces. Such
volume covered entirely the channel of one OTFT and beyond. After the
organic solution deposition, the devices were left overnight in ambient
condition in order to remove residual solvent prior electrical
measurements. A post-annealing step from 50 to 80°C was applied to all
devices in order to increase the microstructural order of thin films. Current-
voltage characteristics were recorded at room temperature under ambient
conditions with Hewlett-Packard 4140B, or 4145A, pico-amperemeter-DC
voltage sources. The source-drain current (ID) in the saturation regime is
governed by the equation (2):
'ZRGTKOGPVCNꢀUGEVKQPꢀ
General Remarks
All reagents were purchased from Acros, Alfa Aesar or Aldrich and were
used without further purification unless otherwise stated. Toluene was
distilled from sodium and benzophenone. Dichloromethane, hexane and n-
heptane were distilled from calcium hydride. Dichloromethane stabilized by
methanol was used during the preparation of OFETs. Silica gel plates
Merck 60 F254 were used for Thin Layer Chromatography (TLC). Silica gel
60 (230-400 mesh) was used for preparative column chromatography.
Flash column chromatography was performed on silica gel 60 (230-400
mesh). (3,5-bis(dodecyloxy)phenyl)methanol,23, Cor115 and Cor216a were
prepared and purified according to literature procedure.
Spectroscopic and analytical measurements
(2) (ID)sat = (W/2L) Ciμ(VG-Vt)2
1H Nuclear Magnetic Resonance (NMR) spectra were recorded on a
Bruker Avance 400 Ultrashield NMR spectrometer. Chemical shifts are
given in ppm relative to residual peaks of chloroform (G = 7.26 ppm),
DMSO-d6 (G = 2.50 ppm) or THF-d8 (G = 1.73 and 3.58 ppm).
Ci is the capacitance per unit area of the gate insulator layer, VG is the
gate voltage, Vt is the threshold voltage, and μ is the field-effect mobility.
The on/off ratio values were determined from the I-V transfer plots under a
constant drain-source voltage VD = -100 V.
UV/Vis absorption spectra were measured with a Shimadzu UV-2401 (PC)
instrument or with a Varian Cary 1E spectrophotometer.
Organic syntheses.
Pneumatically-assisted electrospray (ESI-MS) mass spectra were recorded
from 10-4 M solutions on an Applied Biosystems API 150EX LC/MS
System equipped with a Turbo Ionspray source. High Resolution Mass
Spectrometry (HRMS-ESI) analyses were performed on a QStar Elite
(Applied Biosystems SCIEX) spectrometer or on a SYNAPT G2 HDMS
(Waters) spectrometer. These two instruments are equipped with an
electrospray ionization source and were used within the positive ion mode
and with a capillary voltage set at +5500 V. MALDI-TOFF mass spectra
were obtained on a Voyager Instrument from Applied Biosystems either
with anhydrous glycerol, HABA [2'-(4-hydroxyphenylazo)benzoic acid], or
1,8,9-anthracenetriol (dithranol) matrices.
Compound 1 : (3,5-bis(dodecyloxy)phenyl)methanol (5.00 g, 10.5·mmol)
was dissolved in dry CH2Cl2 (50 mL) and DMF (50 Pl) was added under a
nitrogen atmosphere. A solution of SOCl2 (1.87 g, 15.7·mmol) in dry
CH2Cl2 (50 mL) was added dropwise over a period of 1 hour. The reaction
mixture was stirred at room temperature for 24 hours, evaporated to
dryness and dried under vacuum to provide 1 as a white solid (5.15 g, 10.4
mmol, 99%). 1H NMR (400 MHz, CDCl3): į=0.91 (t, 3J(H, H) = 6.6 Hz, 6H),
1.29-1.50 (m, 36H); 1.75-1.80 (m, 4H), 3.95 (t, 3J(H, H) = 6.5 Hz, 6H), 4.52
(s, 2H), 6.42 (t, 4J(H, H) = 2.5 Hz, 1H), 6.53 (d, 4J(H, H) = 2.5 Hz, 2H). ESI-
MS (CH2Cl2/MeOH 9:1): m/z: (M+.): 495.5; calcd for C31H56ClO2+: 495.4.
CuIII undeca-(4-hydroxyphenyl)corrole: A 1M solution of BBr3 in CH2Cl2
(10 mL, 10 mmol) was added to a solution of Cor2 (45 mg, 29.6 Pmol) in
CH2Cl2 (6 mL) which was stirred at 0 °C for 15 min. The mixture was kept
at 0 °C for 1 h and then stirred at room temperature for 3 days before
CH2Cl2 (20 mL) and CH3OH (10 mL) were added together with an aqueous
saturated solution of NaHCO3 (35 mL). The crude compound was
precipitated by pouring the reaction mixture into water (100 mL). The
precipitates were filtered and purified by chromatography on silica gel
(CH2Cl2/CH3OH, 5:1) to afford 3 as a brown powder (18 mg, 13.1 Pmol,
44%). Rf = 0.11 (CH2Cl2/CH3OH, 4:1). 1H NMR (400 MHz, THF-d8, 25 °C):
G= 7.85 (s, 2H, Ar-OH), 7.83 (s, 3H, Ar-OH), 7.63 (s, 2H, Ar-OH), 7.53 (s,
2H, Ar-OH), 7.47 (s, 2H, Ar-OH), 6.94 (d, 3J(H, H) = 8.4 Hz, 2H, Ar-H), 6.76
(d, 3J(H, H) = 7.9 Hz, 4H, Ar-H), 6.66 (d, 3J(H, H) = 8.4 Hz, 4H, Ar-H), 6.40
(d, 3J(H, H) = 7.6 Hz, 8H, Ar-H), 6.40 (d, 3J(H, H) = 8.0 Hz, 4H, Ar-H), 6.27
(d, 3J(H, H) = 8.5 Hz, 4H, Ar-H), 6.09 (m, 8H, Ar-H), 6.03 (d, 3J(H, H) = 8.6
Hz, 4H, Ar-H), 5.96 (d, 3J(H, H) = 7.5 Hz, 4H, Ar-H), 5.93 ppm (d, 3J(H, H)
Liquid crystals analyses.
TGA was performed with a Seiko TG/DTA 320 thermogravimetric balance
(under N2). DSC traces were recorded with a Mettler Toledo DSC1 Star
Systems differential scanning calorimeter from 3 to 5 mg samples (5 °C
min-1, under N2). Characterization of the mesophases was performed with
a Leitz OrthoplanPol polarizing microscope with a Leitz LL 20x/0.40
polarizing objective and equipped with a Linkam THMS 600 variable
temperature stage. The SA-XRD patterns were obtained with three
different experimental setups, and in all cases, the crude powder was filled
in Lindemann capillaries of 1 mm diameter. (1) A STOE STADI
transmission powder diffractometer system using focused
monochromatic Cu-KĮ1 beam obtained from curved germanium
P
a
a
monochromator (Johann-type) and collected on a curved image-plate
position sensitive detector. A calibration with silicon and copper laurate
standards, for high- and low-angle domains, respectively, was preliminarily
performed. Sample capillaries were placed in the high-temperature
attachment for measurements in the range of desired temperatures (from
20 to 160 °C), for which the sample temperature was controlled within 0.05
°C. The exposure times were varied from 1 to 6 h, depending on the
specific reflections being sought (weaker reflections obviously taking
longer exposure times).
= 8.5 Hz, 2H, Ar-H). UV-Vis (THF): Ȝmax (İ ɯ 10-3)= 468 (83.6), 550 (18.7),
+
643 nm (12.2). MALDI-TOF (M+.): 1370.2; calcd for C85H55CuN4O11
:
1370.3.
CorLC
:
CuIII undeca-(4-hydroxyphenyl)corrole (7.2 ȝmol, 10 mg),
compound 1 (22 equiv., 79.2 ȝmol, 39 mg) and K2CO3 (44 equiv., 158.4
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ȝmol, 22 mg) were added to a round-bottomed flask which was oven dried
overnight at 111 °C. The flask was evacuated and backfilled with argon
three consecutive times. Dry DMF (5 mL) was then charged by a syringe.
The mixture was subsequently stirred at 90 °C for 24 h. After being cooled
to room temperature, the solvent was evaporated under reduced pressure.
The crude product was purified by chromatography on silica gel
(CH2Cl2/heptane, 2:1) to yield CorLC as a viscous oil (11 mg, 1.6 ȝmol,
23%). Rf = 0.64 (CH2Cl2/Hexane, 2:1). 1H NMR (400 MHz, CDCl3, 25 °C):
7
8
N. B. Chaure, C. Pal, S. Barard, T. Kreouzis, A. K. Ray, A. N.
Cammidge, I. Chambrier, M. J. Cook, C. E. Murphy and M. G. Cain,
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e
3
G= 6.97 (d, J(H, H) = 8.6 Hz, 3H, Ar-H), 6.83 (t, 8H, Ar-H), 6.61 (brs, 4H,
Ar-H), 6.51 (d, 3J(H, H) = 8.6 Hz, 4H, Ar-H), 6.47 (m, 13H, Ar-H), 6.42 (t,
8H, Ar-H), 6.38 (m, 4H, Ar-H), 6.35 (m, 10H, Ar-H), 6.35 (m, 13H, Ar-H),
6.27 (d, 3J(H, H) = 8.8 Hz, 4H, Ar-H), 6.17 (d, 3J(H, H) = 7.5 Hz, 4H, Ar-H),
6.12 (d, 3J(H, H) = 8.7 Hz, 2H, Ar-H), 4.80 (s, 4H, ArOCH2Ar), 4.72 (s, 4H,
ArOCH2Ar), 4.70 (s, 4H, ArOCH2Ar), 4.68 (s, 4H, ArOCH2Ar), 4.64 (d, 6H,
ArOCH2Ar), 3.80 (m, 44H, OCH2CH2), 1.68 (m, 44H, OCH2CH2), 1.38 (m,
44H, OCH2CH2CH2), 1.25 (m, 352H), 0.86 ppm (m, 66H, CH3). UV-Vis
(CH2Cl2): Ȝmax (İ ɯ 10-3) = 464 (124.3), 549 (29.4), 639 nm (17.4). MALDI-
TOF (M+.): 6417.5 (Maximum iso); calcd for C426H649CuN4O33+: 6417.9
(Maximum iso); ([M+Na]+): 6440.4; calcd for C426H649CuN4O33Na+: 6440.9.
9
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#EMPQYNGFIGOGPVUꢀ
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Dr. Laure Guénée is acknowledged for SA-XRD
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Scholarship Council for granting him his PHD fellowship in
Marseille.
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0QVGUꢀCPFꢀTGHGTGPEGU
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videlot@cinam.univ-mrs.fr
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c Department of Inorganic and Analytical Chemistry, University of Geneva,
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37 960 69; E-mail: emmanuel.terazzi@unige.ch
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†
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