Synthesis, Spectroscopic Properties, and Structure of [Tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyaninato]metal Complexes

Article abstract of DOI:10.1002/ejic.200300470

A series of highly soluble [tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyaninato]metal complexes [MPc(OC ₇H₁₅)₄] (M = Zn, Pd, Co) were prepared by cyclic tetramerization of 3-(2,4-dimethyl-3-pentyloxy)phthalonitrile (2) in t

Full text of DOI:10.1002/ejic.200300470

FULL PAPER
Synthesis, Spectroscopic Properties, and Structure of [Tetrakis(2,4-dimethyl-3-
pentyloxy)phthalocyaninato]metal Complexes
[a]
[a]
[a]
[a]
Wei Liu, Chi-Hang Lee, Hoi-Shan Chan, Thomas C. W. Mak, and
Dennis K. P. Ng*[
a]
Keywords: Macrocyclic compounds / Inclusion compounds / N ligands
A series of highly soluble [tetrakis(2,4-dimethyl-3-pentyl-
oxy)phthalocyaninato]metal complexes [MPc(OC ] (M =
Zn, Pd, Co) were prepared by cyclic tetramerization of 3-(2,4-
dimethyl-3-pentyloxy)phthalonitrile (2) in the presence of the complexes and the C
of the metal-free phthalocyanine H
treating 2 with CeCl and DBU in n-pentanol. The structures
of the C4h isomers of the (phthalocyaninato)zinc and -cobalt
isomer of the manganese analogue
2 7 15 4
Pc(OC H ) formed by
7
H
15
)
4
3
4
corresponding metal salts and 1,8-diazabicyclo[5.4.0]undec-
-ene (DBU) in n-pentanol. For M = Zn and Pd, two major
isomers with a C4h and C2v symmetry were isolated by
column chromatography and characterized with various
spectroscopic methods, while the cobalt analogue showed
only the C4h isomer. The (phthalocyaninato)manganese com-
were also established by X-ray diffraction analyses. The pal-
ladium counterpart formed a novel 1:1 inclusion complex
with oxalic acid, the crystal structure of which was also deter-
mined.
7
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
plex [MnClPc(OC
7
H
15
)
4
] was also synthesized by metallation
Germany, 2004)
Introduction
anines containing these substituents have been briefly re-
ported for use as optical recording materials.
[
7]
Phthalocyanines are traditional pigments that were disco-
vered almost a century ago. They are a unique class of Results and Discussion
macrocyclic compounds, with intriguing physical and
chemical properties that allow their use in many disci- Synthetic Studies
[
1]
plines. Their well-documented functions as molecular
In the synthesis of these (phthalocyaninato)metal com-
plexes (Scheme 1) 3-nitrophthalonitrile (1) is treated with
[2]
opto-electronic materials, photosensitizers for photodyn-
amic therapy, and catalysts for oxidative degradation of
[
3]
[
4]
pollutants are still being actively exploited. For some of
these applications, highly soluble and non-aggregated
phthalocyanines are desirable. The former property facili-
tates the purification and the fabrication processes, while
the latter assists in characterization and allows these materi-
als to function properly; many properties of phthalocyan-
ines change upon aggregation.[5] As a result, a substantial
number of phthalocyanines with sterically demanding sub-
stituents have been reported.[ We describe herein a series
of (phthalocyaninato)metal complexes substituted with four
6]
2,4-dimethyl-3-pentyloxy groups. These bulky and hydro-
phobic substituents not only enhance the solubility of
phthalocyanines in organic solvents and reduce their tend-
ency to aggregate, but also facilitate the separation of the
isomers of tetra-α-substituted phthalocyanines. Phthalocy-
[
a]
Department of Chemistry, The Chinese University of Hong
Kong,
Shatin, N. T., Hong Kong, China
Fax: (internat.) ϩ 852-2603-5057
E-mail: dkpn@cuhk.edu.hk
Scheme 1. Preparation of [tetrakis(2,4-dimethyl-3-pentyloxy)-
phthalocyaninato]zinc, -palladium, and -cobalt complexes
286
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DOI: 10.1002/ejic.200300470
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[Tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyaninato]metal Complexes
FULL PAPER
2
,4-dimethyl-3-pentanol in the presence of K CO in DMF
2 3
to afford 3-(2,4-dimethyl-3-pentyloxy)phthalonitrile (2).
Cyclization of 2 with zinc() acetate or palladium() chlo-
ride in the presence of DBU in n-pentanol then furnishes
the corresponding (phthalocyaninato)metal complexes.
Only the C4h and C2v isomers could be isolated by column
chromatography, while the D2h and C isomers were not de-
s
tected. For the (phthalocyaninato)zinc complexes, the C4h
isomer 3 was eluted first followed by the C2v isomer 4.
Interestingly, this order was reversed for the palladium ana- Scheme 2. Preparation of (phthalocyaninato)manganese complex 9
logues 5 and 6. These isomers are usually separated by me-
dium- or high-pressure liquid chromatography,[ but their
facile separation here may be attributed to the bulky 2,4-
dimethyl-3-pentyloxy substituents at the α-positions. It is
tra, due to the relief of aggregation by the axial coordi-
also noteworthy that for both the zinc and palladium ana-
8]
zinc analogues 3 and 4 in CDCl were sharpened upon ad-
3
dition of a drop of [D ]pyridine to give well-resolved spec-
5
[
12]
nation of the zinc() center by pyridine.
The spectra for
logues the C2v isomer is produced in higher yield than the
C4h counterpart, which is supposed to be thermo-
dynamically more stable. This cannot be explained by the
alkoxide-induced sequential nucleophilic attack of
the palladium analogues 5 and 6 were well resolved even in
1
the absence of [D ]pyridine. Figure 1 (b) shows the
H
5
NMR spectrum of 5 in CDCl , in which all the signals can
3
be assigned unambiguously. The spectrum shows a doublet
at δ ϭ 9.05 ppm, an overlapping doublet of doublets (or
virtual triplet) at δ ϭ 8.03 ppm, and a doublet at δ ϭ
[
9]
phthalonitriles and the ‘‘template’’ mechanism proposed
[
8b]
by Hanack et al.,
which will give predominantly the C4h
and C isomers, respectively. The reaction mechanism re-
s
7.68 ppm for the three sets of ring protons. The four equiva-
mains elusive but, as reported earlier,[ the isomer distri-
bution of tetra-α-substituted (phthalocyaninato)metal com-
plexes depends on many factors, including the nature of the
substituent, reaction conditions, and metal center. Further
investigation is clearly required.
8b]
lent 2,4-dimethyl-3-pentyloxy groups resonate at δ ϭ 4.67
(t, OCH), 2.54Ϫ2.64 (m, CH), 1.48 (d, Me), and 1.19 ppm
(d, Me). All these signals are split for compound 6 [Figure 1
(a)], which clearly confirms its C2v symmetry.
The cobalt counterpart 7, prepared similarly using CoCl2
as the metal salt, was unstable on silica gel: the blue color
faded gradually during chromatography. Preliminary purifi-
cation could, however, be achieved by flash chromatogra-
phy through a short column packed with neutral alumina.
Further purification by recrystallization led to the pure C4h
isomer 7, which was confirmed by single-crystal X-ray
analysis. Other constitutional isomers, which were probably
also formed during the reaction, could neither be isolated
1
nor detected by H NMR spectroscopy due to the paramag-
netic cobalt() center.
Our recently reported cerium-promoted method to pre-
pare metal-free phthalocyanines afforded high yields of
1
(
,8,15,22-tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyanine
8),[ which can be used to prepare (phthalocyaninato)me-
10]
tal complexes. Thus, while treatment of the dinitrile 2 with
Mn(OAc) ·2H O and DBU in n-pentanol yielded a dark
2
2
brown solution which did not show the typical phthalocy-
anines’ Q-band absorption, compound 8 could be metal-
lated with Mn(OAc) ·2H O in DMF to give the (phthalocy-
2
2
aninato)manganese() complex 9 in 88% yield (Scheme 2).
The manganese() ion was oxidized during the reaction and
the axial chloro ligand came from the brine used during the
workup procedure. Similar results were also observed dur-
ing the preparation of (chloro)(porphyrazinato)mangane-
1
Figure 1. H NMR spectra of 6 (a) and 5 (b) in CDCl
3
; * water
[
11]
se() complexes.
signal
Spectroscopic Properties
The (phthalocyaninato)metal complexes 3Ϫ7 and 9 gave
The C4h and C2v isomers of the (phthalocyaninato)zinc typical UV/Vis absorptions of phthalocyanines (Table 1).
and -palladium complexes could be distinguished readily by The absorption data of the C4h and C2v isomers of the
1
H NMR spectroscopy. The rather broad signals for the (phthalocyaninato)zinc and -palladium complexes do not
Eur. J. Inorg. Chem. 2004, 286Ϫ292
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287

W. Liu, C.-H. Lee, H.-S. Chan, T. C. W. Mak, D. K. P. Ng
FULL PAPER
Table 1. UV/Vis data for (phthalocyaninato)metal complexes 3Ϫ7 and 9 in CHCl
3
Compound
λ
max [nm] (log ε)
Vibronic band(s)
B-band
LMCT
Q-band
Zn[Pc(OC
Zn[Pc(OC
7
7
H
H
15
)
)
4
] (3)
] (4)
] (5)
] (6)
322 (4.54)
323 (4.59)
314 (4.31)
314 (4.44)
313 (3.86)
337 (4.18)
Ϫ
Ϫ
Ϫ
Ϫ
638 (4.37)
638 (4.41)
623 (4.36)
625 (4.46)
631 (3.66)
693 (3.93)
Ϫ
Ϫ
711 (5.13)
709 (5.14)
694 (5.10)
696 (5.19)
702 (4.31)
775 (4.67)
15
4
Pd[Pc(OC
Pd[Pc(OC
7
H
H
15
)
)
4
664 (4.08)
671 (4.44)
Ϫ
Ϫ
7
15
4
Co[Pc(OC
MnCl[Pc(OC
7
H
15
)
4
] (7)
] (9)
Ϫ
7
H
15
)
4
550 (3.85)
show significant differences. The Q-band position, however, Structural Studies
II
is highly dependent on the metal center in the order Pd Ͻ
Co Ͻ Zn ϽϽ Mn . The (phthalocyaninato)manganese
II
II
III
Both the zinc and cobalt phthalocyanines 3 and 7 co-
complex 9 is brown instead of the characteristic blue-green crystallize with a water molecule, which may come from the
as a result of the very long Q-band absorption (775 nm), solvents used for recrystallization. In the molecular struc-
which appears to be the longest wavelength recorded for ture of 3 the zinc atom is disordered about the inversion
(
phthalocyaninato)metal complexes. This remarkably large center relating the two halves of the molecule (Figure 2).
red-shift may be attributed to the effects of metal center The oxygen atom of water occupies a site with half occu-
˚
and the electron-donating alkoxy substituents introduced at pancy, giving the shortest ZnϪO distance at 2.034 A, which
[
14]
the α-positions. A characteristic ligand-to-metal charge- may be regarded as axial ligation.
transfer (LMCT) band at 550 nm was also seen for 9.
The corresponding
CoϪO distance in 7 (2.494 A), however, is significantly
Having four bulky 2,4-dimethyl-3-pentyloxy substituents, longer than typical CoϪOH bonds in (aquo)cobalt()
[
13]
˚
2
˚
[15]
these phthalocyanines are expected to be relatively non-ag- complexes (ca. 2.1Ϫ2.2 A).
gregated in solutions. This was confirmed by variable-con-
Both 3 and 7 crystallize in the monoclinic system with
centration UV/Vis studies of compounds 3, 5, and 9 in two molecules per unit cell. The phthalocyanine rings are
[
16]
CHCl . For these three compounds, plots of the Q-band arranged in a herringbone manner
along the crystallo-
3
Ϫ7
absorbance versus concentration (from 2 ϫ 10 to 3 ϫ graphic b axis with a stacking angle of 54.1 (3) or 59.7° (7)
mol·dm ) gave perfect straight lines, showing that the and an interplanar distance of 6.98 (3) or 7.40 A (7) (Fig-
compounds strictly follow the LambertϪBeer law. This ure 3). This arrangement is similar to that of the metal-free
Ϫ5
Ϫ3
˚
10
[
10a]
[17]
indicates that the compounds exist mainly in monomeric analogue 8
and the unsubstituted phthalocyanine.
form under the conditions employed. The zinc complexes 3 Due to the bulky 2,4-dimethyl-3-pentyloxy substituents,
and 4, however, are slightly aggregated at higher concen- which act as spacers, the interplanar distances for these sub-
Ϫ3
Ϫ3
trations (ca. 10 mol·dm ) as shown by NMR studies stituted phthalocyanines are much larger than that of the
˚
(see above).
unsubstituted counterpart (3.31 A).
Figure 2. Molecular structure of 3 showing the 30% probability thermal ellipsoids for all non-hydrogen atoms; the zinc atom is disordered
˚
2
distance at 2.034 A
with the shortest ZnϪOH
288
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[Tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyaninato]metal Complexes
FULL PAPER
˚
[
Mn(TPP)Cl] (2.02 A). This is in agreement with the larger
central cavity of the TPP ring. The MnϪCl distance in 9
2.343 A) is significantly shorter than that in [Mn(OES-
(
˚
˚
TAP)Cl] (2.394 A) and [Mn(TPP)Cl] (2.37 A). Due to the
square-pyramidal structure and the C disposition of the
4
substituents, compound 9 can exhibit chirality. That the
compound crystallizes in the orthorhombic system with a
P2 2 2 space group shows that the crystal contains only
1
1 1
one of the enantiomers, although a racemic mixture is ex-
pected to form during the reaction. This compound is thus
a rare example of a structurally characterized manganese
[
20]
complex
metry.
and phthalocyanine with a planar asym-
[
21]
We have recently reported a novel 1:1 inclusion complex
of the metal-free phthalocyanine 8 and oxalic acid gener-
ated unexpectedly in a cerium-promoted cyclization reac-
[
10a]
tion.
The crystal structure shows that the oxalic acid
molecules are intercalated between the phthalocyanine rings
and not be hydrogen-bonded in any conventional or uncon-
ventional manner. This is very unusual for molecules, such
as oxalic acid, which have good hydrogen-bonding func-
2
Figure 3. Packing of 3·H O viewed along the a axis; all hydrogen
atoms omitted for clarity
[
22]
In the (phthalocyaninato)manganese complex 9 the tionalities. To further explore this novel class of inclusion
manganese center is coordinated by four isoindole nitrogen complexes, the (phthalocyaninato)palladium complex 5 was
atoms of the phthalocyanine ring and one terminal chloro recrystallized in the presence of 1 equiv. of oxalic acid, giv-
ligand, forming a slightly distorted square pyramid (Fig- ing the 1:1 inclusion complex 5·C H O . The IR spectrum
2
2
4
Ϫ1
ure 4). In contrast to the zinc and cobalt analogues, in of 5·C H O (KBr) showed a strong band at 1671 cm and
which the metal center lies in the isoindole N plane, the a medium band at ca. 3400 cm , which can be ascribed to
2
2
4
Ϫ1
4
˚
manganese atom is displaced 0.291 A above the N plane the CϭO and OϪH stretches, respectively, of the oxalic
4
towards the apical chloro ligand. The displacement is simi- acid. Figure 5 depicts the packing of molecules in the lattice
˚
lar to that in [Mn(OESTAP)Cl] [0.291 A; OESTAP ϭ viewed along the crystallographic a and b axes, which shows
2
,3,7,8,12,13,17,18-octakis(ethylsulfanyl)-meso-tetraaza- that the guest species are not hydrogen-bonded and simply
[
18]
˚
porphyrinate],
but is 0.03 A longer than that in hang between the phthalocyanine rings. The polar oxalic
[
19]
[
Mn(TPP)Cl] (TPP ϭ meso-tetraphenylporphyrinate).
acid preferentially resides in the more polar cavity between
˚
The average MnϪN(isoindole) distance (1.960 A) is also the phthalocyanine rings rather than in bulk CHCl . The
3
similar to the average MnϪN(pyrrole) distance of [Mn- stacking angle is 54.3° and the interplanar distance is 7.13
˚
˚
(
OESTAP)Cl] (1.951 A), but shorter than that in A, which are similar to those of 3 and 7. The oxalic acid
Figure 4. Molecular structure of 9 showing the 30% probability thermal ellipsoids for all non-hydrogen atoms
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289

W. Liu, C.-H. Lee, H.-S. Chan, T. C. W. Mak, D. K. P. Ng
FULL PAPER
Figure 6. Molecular structure of the disordered oxalic acid in
˚
5
·C
2
H
2
O
4
; selected bond lengths [A] and angles [°]: C(31)ϪC(31A)
1
.566(10), C(31)ϪO(4) 1.142(16), C(31)ϪO(3) 1.204(18),
C(32)ϪC(32A) 1.572(10), C(32)ϪO(4A) 1.176(16), C(32)ϪO(3)
1.229(18); O(4)ϪC(31)ϪO(3) 140.7(13), O(4)ϪC(31)ϪC(31A)
129(2), O(3)ϪC(31)ϪC(31A) 89.7(17), O(4A)ϪC(32)ϪO(3)
147.5(13), O(4A)ϪC(32)ϪC(32A) 125(2), O(3)ϪC(32)ϪC(32A)
87.7(16)
cations were performed on silica gel columns (MachereyϪNagel,
0Ϫ230 mesh) with the indicated eluents unless otherwise stated.
Hexane used in chromatography was distilled from anhydrous
CaCl . All other reagents and solvents were of reagent grade and
used as received. The preparation of the metal-free phthalocyanine
7
2
8
has been reported previously.[
recorded with a Bruker DPX 300 spectrometer ( H: 300 MHz; C:
5.4 MHz) in CDCl solutions unless otherwise stated. Chemical
shifts are relative to internal SiMe (δ ϭ 0 ppm). IR spectra were
10] 1
H and C NMR spectra were
13
Figure 5. Crystal structure of 5·C
2
H
2
O
4
: views along the a (a) and
1
13
b axis (b); all hydrogen atoms omitted for clarity
7
3
4
molecule is disordered (Figure 6). The average CϪC, Cϭ measured with a Nicolet Magna 550 FT-IR spectrometer as KBr
˚
pellets. UV/Vis spectra were taken with a Cary 5G UV/Vis/NIR
spectrophotometer. Liquid secondary-ion (LSI) mass spectra were
recorded with a Bruker APEX 47e Fourier transform ion cyclotron
resonance (FTICR) mass spectrometer with a 3-nitrobenzyl alcohol
matrix. Elemental analyses were performed by Medac Ltd., Brunel
Science Centre, UK.
O, and CϪO bond lengths are 1.569, 1.159, and 1.217 A,
respectively. The latter two are significantly shorter than the
corresponding values for hydrogen-bonded oxalic acid (ca.
˚
.20 and 1.31 A).
[23]
1
Conclusion
3
-(2,4-Dimethyl-3-pentyloxy)phthalonitrile (2):[24] A mixture of 3-
We have prepared and characterized a series of (phthalo- nitrophthalonitrile (1) (2.0 g, 12 mmol), 2,4-dimethyl-3-pentanol
(
2 3
4.8 g, 41 mmol), and K CO (12.6 g, 91 mmol) in DMF (20 mL)
cyaninato)metal complexes substituted with four bulky 2,4-
dimethyl-3-pentyloxy groups. The C4h isomers of the
was heated at 65 °C for 2 d. The mixture was then poured into ice-
cold water (200 mL) to give a light brown solid, which was filtered
off and dissolved in CHCl
dried with anhydrous MgSO
3
residue was chromatographed with CHCl as eluent to give the
(phthalocyaninato)zinc and -cobalt complexes and the C4
3
(20 mL). The resultant solution was
and then concentrated in vacuo. The
isomer of the manganese analogue have been structurally
characterized. The palladium counterpart forms a rare 1:1
inclusion complex, with oxalic acid, the structure of which
has also been determined.
4
product as a white solid. Further purification was achieved by
recrystallization with hexane to afford white shiny needles (2.4 g,
8
18 2
4%), m.p. 82Ϫ83 °C. C15H N O (242.3): calcd. C 74.34, H 7.49,
1
N 11.57; found C 74.43, H 7.28, N 11.62. H NMR: δ ϭ 7.50Ϫ7.55
(m, 1 H, ArH), 7.21Ϫ7.24 (m, 2 H, ArH), 4.00 (t, J ϭ 6.0 Hz, 1
H, OCH), 2.02Ϫ2.11 (m, 2 H, CH), 0.94 (d, J ϭ 6.9 Hz, 6 H, Me),
Experimental Section
1
3
1
General Remarks: Reactions were performed under nitrogen. n-
Pentanol and THF were distilled from sodium and sodium/benzo-
phenone ketyl, respectively. DMF was predried with barium oxide
and distilled under reduced pressure. Chromatographic purifi-
0.88 (d, J ϭ 6.9 Hz, 6 H, Me) ppm. C{ H} NMR: δ ϭ 163.3,
134.3, 124.5, 117.8, 117.1, 115.4, 113.3, 105.0, 90.9, 30.5, 19.8,
Ϫ1
17.4 ppm. IR (KBr): ν˜ ϭ 2225 m cm (CϵN). HRMS (EI): m/z
ϩ
18 2
calcd. for C15H N O [M ] 242.1419, found 242.1435.
290
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[Tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyaninato]metal Complexes
FULL PAPER
[
4
Tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyaninato]zinc(II) (3 and
eluent. The crude product obtained was further purified by chro-
matography again using the same eluent to develop two blue bands.
):
A
mixture of the dinitrile
2
(100 mg, 0.41 mmol),
Zn(OAc)
2
·2H O (32 mg, 0.15 mmol), and DBU (0.2 mL) in n- The first band was collected and the solvents were evaporated to
2
pentanol (3 mL) was heated at 160 °C for 8 h. The volatiles were
then removed in vacuo and the residue was chromatographed with
hexane/ethyl acetate (2:1) as eluent. A green band was collected
and the solvents were evaporated to give a crude isomeric mixture
give the C4h isomer 7 as a green solid (35 mg, 34%), which could
be recrystallized by layering MeOH onto a CHCl solution. The
second band contained about 5 mg of material, which could not
3
be further purified by recrystallization because of its instability in
ϩ
of [ZnPc(OC
using CHCl
7
H
15
)
4
], which was further purified by chromatography
8 4
solutions. HRMS (LSI): m/z calcd. for C60H72CoN O [M ]
3
/ethyl acetate (10:1) as eluent. Two green bands were
1027.5008, found 1027.4739.
then developed which were collected separately to give the C4h iso-
Chloro[1,8,15,22-tetrakis(2,4-dimethyl-3-pentyloxy)phthalo-
cyaninato]manganese(III) (9): A mixture of the metal-free phthalo-
mer 3 (20 mg, 19%) and the C2v isomer 4 (59 mg, 55%), respectively.
1
3
7
7
: H NMR (CDCl
3
with a drop of [D
), 7.95 (t, J ϭ 7.5 Hz, 4 H, Pc-H
), 4.61 (t, J ϭ 5.7 Hz, 4 H, OCH), 2.50Ϫ2.60
5
]pyridine): δ ϭ 9.06 (d, J ϭ
cyanine 8 (50 mg, 0.05 mmol) and Mn(OAc)
.05 mmol) in DMF (3 mL) was heated at 60 °C for 4 h. Water
10 mL) was then added and the resulting mixture was washed with
2 2
·2H O (10 mg,
.5 Hz, 4 H, Pc-H
.5 Hz, 4 H, Pc-H
a
b
), 7.61 (d, J ϭ
0
(
c
(
2
m, 8 H, CH), 1.47 (d, J ϭ 6.6 Hz, 24 H, Me), 1.14 (d, J ϭ 6.6 Hz,
4 H, Me) ppm. 1 C{ H} NMR (CDCl
3
1
hexane (3 ϫ 15 mL) to remove unchanged 8. The obtained brown
aqueous layer was mixed with saturated brine (5 mL), and the mix-
with a drop of [D ]pyrid-
3 5
ine): δ ϭ 158.7, 153.8, 143.9, 142.0, 129.8, 125.8, 114.7, 113.6, 89.7,
1.2, 20.2, 18.4 ppm. HRMS (LSI): m/z calcd. for C60 Zn
with a
and Pc-HaЈ),
and Pc-HbЈ), 7.59Ϫ7.68 (m, 4 H, Pc-H
and Pc-HcЈ), 4.66 (t, J ϭ 6.0 Hz, 2 H, OCH), 4.27 (t, J ϭ 6.0 Hz,
ture was then extracted with CHCl
reddish-brown extracts were dried with anhydrous MgSO
3
(3 ϫ 15 mL). The combined
and the
3
73 8 4
H N O
ϩ
1
4
[
MH ] 1033.5046, found 1033.5182. 4: H NMR (CDCl
drop of [D ]pyridine): δ ϭ 9.03Ϫ9.11 (m, 4 H, Pc-H
.93Ϫ8.04 (m, 4 H, Pc-H
3
solvents evaporated in vacuo to give a brown residue, which was
purified by column chromatography on neutral alumina using hex-
ane/ethyl acetate (4:1) as eluent. The crude product was further
purified by recrystallization from hexane/THF to give brown
5
a
7
b
c
2
1
H, OCH), 2.52Ϫ2.64 (m, 4 H, CH), 2.28Ϫ2.39 (m, 4 H, CH),
.49Ϫ1.53 (m, 24 H, Me), 1.17 (d, J ϭ 6.6 Hz, 12 H, Me), 0.73 (d,
needles (48 mg, 88%). C64
8 5
H80ClMnN O (9·THF): calcd. C 67.93,
H 7.13, N 9.91; found C 67.84, H 7.03, N 9.77. HRMS (LSI): m/z
J ϭ 6.6 Hz, 12 H, Me) ppm. HRMS (LSI): m/z calcd. for
ϩ
ϩ
calcd. for C60
H72MnN
8
O
4
[M Ϫ Cl] 1023.5057, found 1023.4670.
C
60
H
73
N
8
O
4
Zn [MH ] 1033.5046, found 1033.5181.
X-ray Crystallographic Analyses of 3·H
2
O, 5·C , 7·H O and
2
H
2
O
4
2
[
(
(
Tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyaninato]palladium(II
)
9
·H O·THF: Single crystals of 3·H O and 7·H
layering MeOH onto a CHCl solution of 3 or 7. By adding oxalic
acid in the MeOH layer, single crystals of 5·C were obtained
similarly. Single crystals of 9·H O·THF were obtained by layering
2
2
2
O were obtained by
5 and 6): A mixture of the dinitrile 2 (100 mg, 0.41 mmol), PdCl
2
3
21 mg, 0.12 mmol), and DBU (0.2 mL) in n-pentanol (3 mL) was
2
2 4
H O
heated at 140 °C for 18 h. The volatiles were then removed in vacuo
and the residue was subjected to chromatography using CHCl as
eluent. The crude product was chromatographed again with hex-
ane/CHCl (2:1) as eluent to develop two green bands, which were
collected and the solvents evaporated. The first band was found to
be the C2v isomer 6 (26 mg, 23%), while the second band was the
2
3
hexane onto a THF solution of 9. Crystal data and details of data
collection and structure refinement are given in Table 2. Data col-
lection for all these compounds was performed with a Bruker
3
SMART CCD diffractometer with Mo-K
α
radiation (λ ϭ 0.71073
˚
A) in a sealed tube at 293 K, using an ω-scan mode with an in-
crement of 0.3°. Preliminary unit cell parameters were obtained
from 45 frames. Final unit cell parameters were derived by global
refinements of reflections obtained from integration of all of the
frame data. The collected frames were integrated by using the pre-
liminary cell-orientation matrix. The following software was em-
ployed: SMART to collect frames of data, index reflections, and
determine the lattice constants; SAINT-PLUS to integrate the
C
4h isomer 5 (18 mg, 16%), which could be further purified by
recrystallization from CHCl /MeOH. 5: Pd
5·CHCl ): calcd. C 61.39, H 6.17, N 9.40; found C 60.34, H 6.32,
3
61 3 8 4
C H73Cl N O
(
3
1
N 9.24. H NMR: δ ϭ 9.05 (d, J ϭ 7.5 Hz, 4 H, Pc-H
J ϭ 7.5, 8.1 Hz, 4 H, Pc-H ), 7.68 (d, J ϭ 8.1 Hz, 4 H, Pc-H
.67 (t, J ϭ 5.7 Hz, 4 H, OCH), 2.54Ϫ2.64 (m, 8 H, CH), 1.48 (d,
a
), 8.03 (dd,
b
c
),
4
J ϭ 6.6 Hz, 24 H, Me), 1.19 (d, J ϭ 6.6 Hz, 24 H, Me) ppm.
1
3
1
C{ H} NMR: δ ϭ 158.6, 154.7, 143.1, 141.4, 130.6, 124.2, 114.7,
[25]
intensity of reflections and for scaling; SADABS for absorption
1
C
13.7, 89.5, 31.4, 20.4, 18.5. HRMS (LSI): m/z calcd. for
[26]
correction; and SHELXL for space group and structure determi-
ϩ
1
60
H
73
N
8
O
4
Pd [MH ] 1075.4783, found 1075.4870. 6: H NMR:
or Pc-HaЈ), 9.03 (d, J ϭ 7.5 Hz,
or Pc-HaЈ), 7.98Ϫ8.06 (m, 4 H, Pc-H and Pc-HbЈ),
.64Ϫ7.69 (m, 4 H, Pc-H and Pc-HcЈ), 4.69 (t, J ϭ 5.7 Hz, 2 H,
[27]
nation, refinements, graphics, and structure reporting.
CCDC-
δ ϭ 9.09 (d, J ϭ 7.5 Hz, 2 H, Pc-H
2
7
OCH), 4.31 (t, J ϭ 5.7 Hz, 2 H, OCH), 2.57Ϫ2.68 (m, 4 H, CH),
2
a
212501 to -212504 contain the supplementary crystallographic data
H, Pc-H
a
b
for 3·H O, 5·C , 7·H O and 9·H O·THF, respectively. These
2
2
H
2
O
4
2
2
c
data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.)
ϩ 44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
.30Ϫ2.41 (m, 4 H, CH), 1.49Ϫ1.52 (m, 24 H, Me), 1.22 (d, J ϭ
.6 Hz, 12 H, Me), 0.77 (d, J ϭ 6.6 Hz, 12 H, Me). 13C{ H} NMR:
1
6
δ ϭ 160.0, 158.6, 154.0, 152.0, 143.2, 143.0, 140.0 (2 overlapping
signals), 130.6, 130.4, 124.2 (2 overlapping signals), 117.0, 115.0,
Acknowledgments
1
14.4, 113.9, 94.2, 89.4, 31.4, 29.7, 20.4, 19.9, 18.4, 18.3 ppm.
ϩ
HRMS (LSI): m/z calcd. for C60
H
73
N
8
O
4
Pd [MH ] 1075.4783, We thank Ms. Hung-Wing Li for technical assistance in the diffrac-
tion analyses. This work was supported by The Chinese University
found 1075.5037.
of Hong Kong and the Hong Kong Research Grants Council.
[
1,8,15,22-Tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyaninato]-
cobalt(II) (7): A mixture of the dinitrile 2 (100 mg, 0.41 mmol), an-
hydrous CoCl (13 mg, 0.10 mmol), and DBU (0.2 mL) in n-penta-
[1] [1a]
Phthalocyanines Ϫ Properties and Applications, vols. 1Ϫ4
Eds: C. C. Leznoff, A. B. P. Lever), VCH, New York,
2
(
nol (3 mL) was heated under reflux overnight. The volatiles were
then removed in vacuo and the residue was subjected to flash chro-
matography on neutral alumina using hexane/ethyl acetate (1:4) as
[1b]
1
989؊1996.
N. B. McKeown, Phthalocyanine Materials:
Synthesis, Structure and Function, Cambridge University Press,
Cambridge, 1998.
Eur. J. Inorg. Chem. 2004, 286Ϫ292
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
291

W. Liu, C.-H. Lee, H.-S. Chan, T. C. W. Mak, D. K. P. Ng
Table 2. Crystallographic data for (phthalocyaninato)metal complexes 3, 5, 7, and 9
·H 5·C
FULL PAPER
3
2
O
2
H
2
O
4
7·H
2
O
2
9·H O·THF
Empirical formula
Formula mass
Crystal size [mm]
Crystal system
Space group
C
60
H
74
N
8
O
5
Zn
C
62
H
74
N
8
O
8
Pd
C
60
H
74CoN
8
O
5
C
64
H
82ClMnN
8 6
O
1052.64
0.22 ϫ 0.18 ϫ 0.14
monoclinic
P2
16.024(4)
8.619(2)
21.726(5)
99.661(5)
2958.0(12)
2
1165.69
0.34 ϫ 0.32 ϫ 0.20
monoclinic
P2
15.8995(8)
8.7861(4)
21.5407(10)
100.3590(10)
2960.1(2)
2
1046.20
0.42 ϫ 0.23 ϫ 0.20
monoclinic
P2
16.015(3)
8.5760(10)
21.708(3)
99.493(4)
2940.6(8)
2
1149.77
0.35 ϫ 0.19 ϫ 0.17
orthorhombic
1 1 1
P2 2 2
13.470(3)
31.079(6)
16.002(3)
90
6699(2)
4
1
/c
1
/c
1
/c
˚
a [A]
˚
b [A]
˚
c [A]
β [°]
˚
3
V [A ]
Z
F(000)
D
µ [mm
1120
1.182
0.468
1224
1.308
0.374
1114
1.182
0.345
2448
1.140
0.289
calcd. [mg mϪ3
]
Ϫ1
]
θ range [°]
Reflections
2.11Ϫ25.00
15498
1.92Ϫ25.00
16002
2.11Ϫ25.00
15482
1.31Ϫ25.00
36485
Unique reflections
Parameters
R1 [I Ͼ 2σ(I)]
wR2 [I Ͼ 2σ(I)]
Goodness of fit
5200 (Rint ϭ 0.0915)
377
0.0917
0.2460
0.918
5213 (Rint ϭ 0.0306)
367
0.0382
0.1050
1.005
5167 (Rint ϭ 0.0857)
326
0.1096
0.2991
1.049
11769 (Rint ϭ 0.2925)
715
0.1087
0.2473
0.913
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[
[
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13]
Received July 16, 2003
[
14]
For the aquo(porphyrinato)zinc() complexes Zn(OH
2
)(TPP)
Early View Article
(
TPP ϭ meso-tetraphenylporphyrinate) and Zn(OH )(TMP)
2
Published Online November 19, 2003
292
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 286Ϫ292