FULL PAPER

DOI: 10.1002/ejic.200801030

Electronic Spectra of Mono- and Dinuclear Complexes of Fully π-Conjugated

salphen Ligands Synthesized by Using 2,6-Dihydroxynaphthalene
Carbaldehydes

Hirohiko Houjou,*[a] Takatoshi Motoyama,[a] and Koji Araki[a]

Keywords: N,O ligands / Through-bond interactions / Transition metals / Conjugation / Molecular electronics

A series of mono- and dinuclear zinc(II), copper(II), nickel(II), complexes exhibited absorbances that were approximately
and iron(III) complexes of novel salphen ligands were syn- twice as intense as those of the [ML1] complexes, as well as
thesized and spectroscopically characterized. The mononu- a 30–50-nm bathochromic shift and considerable extension
clear ligand (H2L1) was synthesized from 2,6-dihydroxynaph- of the low-energy absorption edge relative to the spectrum
thalene-1-carbaldehyde and an o-phenylenediamine; the di- of [ML1]. The spectra of the complexes showed markedly in-
nuclear ligand (H4L2), which was not isolated, contains a 2,6- tensified peaks in various regions, depending on M, which
dihydroxynaphthalene-1,5-dicarbaldimine linkage that en- implies that the effects of extension of π-conjugation were
ables extended π-conjugation over two salphen units. By due to more than simple additivity.
means of a controlled sequence of condensation reactions,
the constituents were built into either mono- ([ML1]) or dinu- (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
clear complexes ([M2L2]). The UV/Vis spectra of the [M2L2] Germany, 2009)

Introduction pπ-conjugated metallopolysalen and polysalphen com-

pounds requires the preparation and analysis of well-de-
Interest in precisely arranging metal atoms has been fined oligonuclear complexes. However, there have been few
growing in connection with the recent development of metal reports[17] highlighting the effects of intracomplex (metal–
cluster chemistry, the coordination space that results from metal and ligand–metal) interactions on the spectroscopic
metal–organic frameworks, and various metallosupramole- features of fully π-conjugated oligonuclear salen and
cular polymers and other metal-containing materials.[1–4] salphen complexes.
Among metallopolymers, systems in which metal atoms are As a part of our continuing works of exploring various
directly bound to an organic main chain with an extended metallopolyimines,[18] we studied carbaldehyde 1 and dicarb-
π-conjugated system are of special interest.[5–7] They can be aldehyde 2 as a component of π-conjugated metallopoly-
expected to show specific properties, such as conductivity, salphen. When these compounds are used as a ligand for a
redox activity, photoluminescence, and magnetism, that metal complex, the electronic state of the metal couples
originate from electronic communication between the metal with that of the π system of the ligand, affording such inter-
atoms mediated by the organic part. The imine linkage is a esting phenomena as metalloaromaticity[19] and valence
promising candidate for the construction of such systems. tautomerism.[20–22] Previously, dioximato complexes of cop-
Of various metallopolyimines, those with salen (N,N⬘-disal- per and nickel were prepared from 2, and these compounds
icylideneethylenediamine) and salphen (N,N⬘-disalicylidene- exhibit semiconducting performance for electronic func-
o-phenylenediamine) ligands have a long history and have tional materials.[23] Despite such promising results, the lit-
been used in various functional materials.[8–13] In addition, erature contains surprisingly few other studies of 1 and 2.
electrolytic polymerization of Ni–salen complexes is inter- Condensation of 2 with diamines would lead to a new class
esting methodology for the fabrication of conductive films, of polynuclear salen and salphens applicable to the prepara-
although the mechanism of conduction (e.g., by an intra- tion of organic electronic device materials. As a primary
chain or interchain carrier path) is still controversial.[14–16] step toward accomplishing this goal, we synthesized and
Clarification of the physicochemical properties of such dπ, characterized novel mono- and dinuclear salphen com-
plexes with 1 and 2. We will describe some interesting spec-
troscopic features that may have originated in the interac-
[a] Institute of Industrial Science, University of Tokyo,
4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan tions of salphen complexes fused into a π-conjugated sys-
E-mail: [email protected] tem.

Eur. J. Inorg. Chem. 2009, 533–538 © 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 533
FULL PAPER H. Houjou, T. Motoyama, K. Araki

comitant metal binding. The products obtained by means

of the two methods were identical to each other, and
method A afforded a slightly higher yield than method B.
The complexes were identified as [ZnL1], [CuL1], [NiL1],
and [FeL1Cl] by IR spectroscopy, fast atom bombardment
mass spectrometry [MS (FAB)], and elemental analysis. The
Zn and Ni complexes were analyzed by 1H NMR spec-
Results and Discussion troscopy ([D5]pyridine). The NMR signals of the nickel
Synthesis of Ligands complex were slightly broadened probably due to the coor-
dination of pyridine molecule(s) in the axial position. The
Monoaldehyde 1,[24] dialdehyde 2,[25] and diamine 3 (R = IR spectra showed a strong peak at 1601–1607 cm–1, which
C12H25)[26] were prepared according to previously reported was assigned to the C=N stretch vibration. The νM–O and
methods. Scheme 1 shows the preparation of mononuclear νM–N bands appeared at 556–584 cm–1 and 419–421 cm–1,
ligand H2L1 and monoimine half-ligand 4. The reaction of respectively, in agreement with the values reported for anal-
diamine 3 with 1 (2.2 equiv.) afforded reddish purple and ogous salphen complexes.[27–30] The overall profiles of
orange crystalline solids, which were identified as H2L1 and [CuL1] and [NiL1] were similar, as were those of [ZnL1] and
4, respectively. The relatively low yield (≈30 %) of H2L1 sug- [FeL1Cl], which suggests that the coordination geometries
gests that the second of the two condensation reactions was of the complexes were similar, that is, square planar (Cu
slow and that 4 separated out before the reaction was com- and Ni) or square pyramidal (Zn and Fe).
plete. A similar reaction carried out under ethanol-rich con- Homodinuclear complexes [M2L2] were synthesized as
ditions afforded mostly 4 (⬎70 %). The reaction of equal shown in Scheme 3. Although we attempted to synthesize
amounts of 1 and 3 afforded mainly 4, but the yield was the dinuclear ligand H4L2 from 4 and 2 by varying the reac-
lower, owing to contamination of the product by unreacted tion parameters, such as the solvent ratio, we were unable
3. The “partial ligand” 4 was then utilized as either a con- to isolate H4L2. Therefore, we utilized the condensation re-
stituent of mono- or dinuclear complexes. action of 2 and 4 with concomitant metal binding (similar
to method B in Scheme 2) to prepare the dinuclear com-
plexes. A similar protocol was utilized to obtain some
double salen and nonsymmetric salen complexes.[31,32]

Scheme 1.

Synthesis of Mono- and Dinuclear Complexes

Mononuclear complexes [ML1], where M = ZnII, CuII,
Ni , or FeIII, were synthesized by one of two methods (A
II

and B, Scheme 2). Method A used H2L1 as a reactant, and

method B involved the condensation of 1 and 4 with con- Scheme 3.

Scheme 2.

534 www.eurjic.org © 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Inorg. Chem. 2009, 533–538
Mono- and Dinuclear Complexes of Fully π-Conjugated salphen Ligands

The complexes were obtained in moderate yields and The spectra of [CuL1] and [Cu2L2] (Figure 1b) are similar
identified as [Zn2L2], [Cu2L2], [Ni2L2], and [Fe2L2Cl2] by to those of [ZnL1] and [Zn2L2], respectively, and again the
IR spectroscopy, MS (FAB), and elemental analysis. The absorption of the latter was nearly twice as intense as that
1
H NMR spectrum ([D5]pyridine) of the Zn complex gave of the former. The peaks of [Cu2L2] at 474 nm
a set of identifiable peaks, whereas the spectrum of the Ni (54900 –1 cm–1) and 536 nm (34200 –1 cm–1) were ba-
complex showed a series of significantly broad signals, thochromically shifted relative to the corresponding peaks
which is again attributable to the coordination of pyridine of [CuL1] at 458 nm (34900 –1 cm–1) and 506 nm
molecule(s). The IR spectra showed stretching bands for (19000 –1 cm–1), respectively; the shoulder at 543 nm
C=N, M–O, and M–N in the regions expected for the esti- (15,700 –1 cm–1) in the spectrum of [CuL1] might corre-
mated structure, and again there was similarity between the spond to the sharp peak at 574 nm (38,100 –1 cm–1) in the
profiles of [Cu2L2] and [Ni2L2], and between those of spectrum of [Cu2L2]. Notably, the spectrum of [Cu2L2] ex-
[Zn2L2] and [Fe2L2Cl2]. hibited a sharper peak at the long-wavelength edge of the
spectrum, as compared to the spectrum of [Zn2L2]. The d–
d transition of CuII complexes is normally observed at
around 600–700 nm, but the corresponding peak was am-
UV/Vis Spectra
biguous for [CuL1] and [Cu2L2], because the peak over-
The electronic absorption spectra in the ultraviolet/vis- lapped substantially with the onset of the absorption.
ible (UV/Vis) region were measured for each of the mono- Similarly, in the spectra of [NiL1] and [Ni2L2] (Fig-
and dinuclear complexes (pyridine, 1 ⫻ 10–4 ). The spectra ure 1c), the absorbance of the dinuclear complex was more
of [ZnL1] and [Zn2L2] were generally similar to each other, than twice that of the mononuclear complex. Intensification
although the absorbance of [Zn2L2] was about 1.5–2 times of the peak in the region of 380–480 nm was significant,
as intense as that of [ZnL1] (Figure 1a). The peaks (with ε and hence, the profiles of the two complexes differed con-
in parentheses) of [Zn2L2] at 461 nm (53600 –1 cm–1) and siderably. The peak for [NiL1] at 440 nm (26600 –1 cm–1)
531 nm (30300 –1 cm–1) were substantially bathochrom- might correspond to the shoulder observed for [Ni2L2] at
ically shifted relative to the corresponding peaks of [ZnL1] 440 nm (72000 –1 cm–1). In the longer-wavelength region,
at 447 nm (41900 –1 cm–1) and 503 nm (23100 –1 cm–1). the peaks for [Ni2L2] at 536 nm (51500 –1 cm–1) and
The prominent peak at 558 nm (31800 –1 cm–1) for [Zn2L2] 569 nm (49600 –1 cm–1) were bathochromically shifted rel-
might correspond to the shoulder at 536 nm ative to the corresponding peaks for [NiL1] at 509 nm
(16800 –1 cm–1) for [ZnL1]. In contrast, the peaks for (20000 –1 cm–1) and 534 nm (19200 –1 cm–1), respectively.
[Zn2L2] at shorter wavelengths (⬍400 nm) were almost un- In contrast to the Cu and Zn complexes, the Ni complexes
changed or were slightly hypsochromically shifted relative did not exhibit sharpening of the peaks at the lower-energy
to those of [ZnL1]. edge of the spectrum. The d–d transitions for both Ni com-
plexes were expected to appear at around 500–600 nm, but
again they were obscured by an intense absorption.
We should note a possibility that the coordination of
pyridine molecule(s) on [NiL1] and [Ni2L2] causes the dif-
ference in the UV/Vis spectra. The NMR spectroscopic re-
sults showed more broadened signals for [Ni2L2] relative to
those for [NiL1], implying that there is a difference in affin-
ity to pyridine molecules. However, because the molecular
environment of the coordination sites is similar, the differ-
ence in line broadening is expected to arise from a kinetic
effect. Namely, during a rapid exchange of the pyridine li-
gand, the more coordination sites a complex has, the longer
period the molecule spends in octahedral coordination re-
sponsible for paramagnetism. Therefore, as far as we mea-
sure steady-state UV/Vis absorption, we can neglect the ef-
fects of solvent coordination. Moreover, the difference in
coordination geometry mainly affects the relative energy
levels of the dx2–y2 and dxy orbitals, which were not likely to
have been involved in the transition of the region of 400–
450 nm. It should rather be taken into account that the ab-
sorption of this region is influenced by the change in π-
conjugated system of salicylidene groups.[27,28]
The spectra of mono- and dinuclear FeIII complexes are
Figure 1. UV/Vis spectra of (a) [ZnL1] and [Zn2L2], (b) [CuL1] and
[Cu2L2], (c) [NiL1] and [Ni2L2], and (d) [FeL1Cl] and [Fe2L2Cl2].
shown in Figure 1d. Although the spectra were measured
The mononuclear ([ML1]) and dinuclear complexes ([M2L2]) are in pyridine solution, we assume that the two iron complexes
denoted by dashed lines and solid lines, respectively. are present as inner-sphere type [FeL1Cl] and [Fe2L2Cl2] as

Eur. J. Inorg. Chem. 2009, 533–538 © 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org 535
FULL PAPER H. Houjou, T. Motoyama, K. Araki

identified in the solid state, as the spectra of similarly pre- rings, whose transition moment is enhanced by the re-
pared complex [Fe(salphen)Cl] in chloroform, less polar duction in the local symmetry of the salen unit. In our case,
and noncoordinative, gave quite a similar absorption profile the intensification of the absorption peak may have arisen
to that of [FeL1Cl]. Further, the similarity between the spec- from the change in transition moment due to the change in
tra of the mono- and dinuclear complexes suggests that they symmetry from C2v (mononuclear complex) to C2h (dinu-
had similar coordination environments. The spectra of the clear complex). According to Glaser et al.[33] such a change
FeIII complexes were markedly broadened relative to those in electronic absorption spectra can be interpreted in terms
of ZnII, CuII, and NiII and the low-energy onset was ex- of the strong electronic communication between the π mo-
tended toward 800–900 nm. The extension was more promi- lecular orbitals of salen units.
nent for the dinuclear system. The absorption of [Fe2L2Cl2]
was nearly double that of [FeL1Cl]. The peak for [Fe2L2Cl2]
at 534 nm (35200 –1 cm–1) was bathochromically shifted Conclusions
relative to the corresponding peak for [FeL1Cl] at 498 nm
We synthesized several mono- and dinuclear complexes
(19600 –1 cm–1), and the peak at 434 nm (30900 –1 cm–1)
of novel π-conjugated salphen ligands. The absorption
in the spectrum of [FeL1Cl] may correspond to the shoulder
peaks of the dinuclear complexes were markedly redshifted
at 442 nm (49600 –1 cm–1) in the spectrum of [Fe2L2Cl2].
relative to the peaks of the mononuclear complexes, and
As was observed for the Ni complexes, the peak at around
there were additional spectral changes beyond simple addi-
380 nm was markedly more intense for the dinuclear system
tivity. For ZnII and CuII, the dinuclear system showed a
than for the mononuclear system.
steep onset at the low-energy edge of the spectrum. For NiII
Comparison of the spectra of the mononuclear com-
and FeIII, the peak at around 380 nm was more intense for
plexes with the spectra of analogous complexes without the
the dinuclear system than for the mononuclear one. No-
6-hydroxy group on the naphthalene ring[27–30] suggests that
tably, the absorption edge of the dinuclear system was ex-
the 6-hydroxy group was responsible for about 30–50 nm of
tended toward the near-infrared region. These changes in
redshift, owing to its electron-donating character; the over-
optical properties are potentially advantageous for applica-
all profiles remained similar. Furthermore, with regard to
tions to optical and optoelectronics materials. Further stud-
the Ni complexes, there was no drastic difference between
ies on the mechanism of the spectral changes and on the
the profiles of salphen and N,N⬘-bis(2-hydroxynaph-
fabrication of polynuclear system are in progress.
thylmethyl-1-ene)-o-phenylenediamine, except for a redshift
of ca. 10 nm for the latter.[27,28] Therefore, we interpret the
absorption profile of the dinuclear complexes as the sum of Experimental Section
the contributions from each salphen moiety.
Definitively assigning the spectra for dπ,pπ-conjugated General: All chemicals and solvents were purchased from Tokyo
systems such as salphen complexes is intrinsically difficult. Kasei Kogyo (TCI) and used without further purification. Monoal-
Because the π(ligand) and π*(ligand) orbitals and the dehyde 1[24] and phenylenediamine 3[26] were prepared according to
literature procedures. Dialdehyde 2 was prepared by the route of
dπ(metal) orbitals mix to form new π(metal + ligand) and
Kuriakose,[25] which was improved by us.[34] UV/Vis absorption
π*(metal + ligand) orbitals, the transitions between them spectra were measured for a pyridine (spectroscopic grade,
cannot be unambiguously characterized as either metal-to- 1 ⫻ 10–4 ) solution of each solute with a JASCO V-630 spectro-
ligand charge transfer (MLCT) or ligand-to-metal charge photometer. NMR spectra were recorded with a JEOL JNM-
transfer.[19] In view of the level of the d orbitals of the first AL400 instrument (400 MHz for 1H). IR spectra were recorded
transition metals, the lowest-energy transition (500–600 nm) with a Shimadzu FTIR-8700 instrument. Melting points were de-
of [ZnL1] was MLCT-like, and the second-lowest transition termined with an optical microscope equipped with a Linkam LK-
(400–500 nm) had ligand-center π–π* transition-like char- 600 temperature-variable stage; the heating rate was 2 K min–1.
acter. Therefore, the overall redshift of the spectra implies H2L1: Monoaldehyde 1 (207 mg, 1.1 mmol) was dissolved in thf
a lowering of the π* level as well as an elevation of the dπ (4 mL), and the solution was added to a thf/methanol solution (1:1,
level. 5 mL) of diamine 3 (239 mg, 0.5 mmol). After 12 h, methanol was
Notably, the changes in absorbance resulting from the added to promote precipitation. The product was filtered, then
fusion of the salphen unit differed from peak to peak, al- washed with methanol, and obtained as a reddish purple crystalline
though the similarity of the overall profiles suggests that solid. Yield: 139 mg (34 %). M.p. 244–246 °C. IR (KBr): ν̃ = 3365
(νO–H), 1611 (νC=N) cm–1. MS (FAB+): m/z = 817.8 [M + H]+.
each peak corresponded to a similar transition for the
C52H68N2O6 (817.08): calcd. C 76.44, H 8.39, N 3.43; found C
mono- and dinuclear systems. The changes in the spectra 76.15, H 8.40, N 3.41. 1H NMR ([D6]DMSO): δ = 0.85 (t, 1J =
may not have only originated from the extension of π conju- 7.3 Hz, 6 H, CH3), 1.20–1.40 (m, 32 H, -CH2-), 1.42–1.51 (m, 4
gation. Recently, suggestive examples were reported by Gla- H, -CH2-), 1.73–1.80 (m, 4 H, -CH2-), 4.15 (t, 1J = 5.9 Hz, 4 H,
ser et al. in studies of Ni, Cu, and V complexes with a -CH2O-), 7.01 (d, 1J = 9.2 Hz, 2 H, ArH), 7.10–7.12 (m, 4 H, ArH),
phloroglucinol-based triple salen.[33] Compared to a “sin- 7.38 (s, 2 H, ArH), 7.76 (d, 1J = 9.3 Hz, 2 H, ArH), 8.39 (d, 1J =
gle” salen complex with C2v symmetry, a triple salen com- 9.7 Hz, 2 H, ArH), 9.54 (br., 2 H, ArOH), 9.56 (s, 2 H, -CH=N-),
plex with C3h symmetry shows a marked increase in ab- 15.05 (br., 2 H, ArOH) ppm.
sorbance in the region of 330–380 nm, which is attributable Partial Ligand 4: Monoaldehyde 1 (753 mg, 4.0 mmol) was dis-
to the π–π* transition of the terminal and central benzene solved in thf/ethanol (1:4, 25 mL), and the solution was added to

536 www.eurjic.org © 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Inorg. Chem. 2009, 533–538
Mono- and Dinuclear Complexes of Fully π-Conjugated salphen Ligands

a thf/ethanol solution (4:3, 35 mL) of diamine 3 (954 mg, 905.6 [M]+. C52H66ClFeN2O6·H2O (924.38): calcd. C 67.56, H 7.41,
2.0 mmol). After 12 h, the mixture was concentrated in vacuo; then, N 3.03; found C 67.44, H 6.83, N 2.80.
methanol (30 mL) was added to promote precipitation. The prod-
[Zn2L2]: To a solution of ligand 4 (129.4 mg, 0.2 mmol) dissolved
uct was obtained as an orange crystalline solid. Yield: 946 mg
in thf (5 mL) was added a thf solution (5 mL) of 2 (21.6 mg,
(73 %). M.p. 140–142 °C. IR (KBr): ν̃ = 3192 (νO–H), 1607 (νC=N)
0.1 mmol). After the solution turned reddish brown, a methanol
cm–1. MS (FAB+): m/z = 647.5 [M + H]+. C41H62N2O4·0.5H2O
solution (3 mL) of zinc acetate dihydrate (48.3 mg, 0.22 mmol) was
(655.93): calcd. C 75.07, H 9.68, N 4.27; found C 74.84, H 9.71, N
added dropwise. After 4 h, the mixture gave a precipitate, which
4.30. 1H NMR ([D6]DMSO): δ = 0.85 (t, 1J = 6.6 Hz, 6 H, CH3),
was collected by filtration and washed with methanol. Reddish pur-
1.19–1.38 (m, 32 H, -CH2-), 1.40–1.48 (m, 4 H, -CH2-), 1.64–1.74
ple crystalline solid. Yield: 127.6 mg (80 %). IR (KBr): ν̃ = 3384
(m, 4 H, -CH2-), 3.90 (t, 1J = 6.3 Hz, 2 H, -CH2O-), 3.95 (t, 1J =
(νO–H), 1607 (νC=N), 569 (νM–O), 415 (νM–N) cm–1. MS (FAB+): m/z
6.4 Hz, 2 H, -CH2O-), 4.76 (s, 2 H, ArNH2), 6.50 (s, 1 H, ArH),
= 1599.7 [M + H]+. C94H124N4O10Zn2·4H2O (1672.82): calcd. C
7.04 (d, 1J = 9.1 Hz, 1 H, ArH), 7.10–7.13 (m, 2 H, ArH), 7.22 (s,
67.49, H 7.95, N 3.35; found C 67.38, H 7.46, N 3.48. 1H NMR
1 H, ArH), 7.72 (d, 1J = 9.1 Hz, 1 H, ArH), 8.41 (d, 1J = 8.8 Hz,
([D5]pyridine): δ = 0.89 (t, 1J = 6.6 Hz, 12 H, CH3), 1.20–1.39 (m,
1 H, ArH), 9.49 (s, 1 H, -CH=N-), 15.43 (s, 1 H, ArOH) ppm.
72 H, -CH2-), 1.48–1.58 (m, 8 H, -CH2-), 1.77–1.87 (m, 8 H,
[ZnL1]: To a solution of H2L1 (40.9 mg, 0.05 mmol) dissolved in -CH2-), 4.18 (t, 1J = 6.4 Hz, 4 H, -CH2O-), 4.22 (t, 1J = 6.3 Hz, 4
thf (5 mL) was dropwise added a methanol solution (1 mL) of zinc H, -CH2O-), 7.48 (d, 1J = 9.3 Hz, 2 H, ArH), 7.51 (d, 1J = 9.2 Hz,
acetate dihydrate (12.1 mg, 0.055 mmol). After 18 h, methanol 2 H, ArH), 7.56 (s, 2 H, ArH), 7.77 (d, 1J = 9.5 Hz, 2 H, ArH),
(6 mL) was added, and the mixture was then concentrated in vacuo 7.85 (s, 2 H, ArH), 7.92 (s, 2 H, ArH), 8.65 (d, 1J = 9.3 Hz, 2 H,
until a solid precipitated. The product was obtained as a reddish ArH), 8.74 (d, 2 H, ArH), 8.83 (d, 1J = 9.3 Hz, 2 H, ArH), 10.16
purple crystalline solid. Yield: 38 mg (86 %). IR (KBr): ν̃ = 3368 (s, 2 H, -CH=N-), 10.20 (s, 2 H, -CH=N-), 11.44 (s, 2 H, ArOH)
(νO–H), 1607 (νC=N), 566 (νM–O), 419 (νM–N) cm–1. MS (FAB+): m/z ppm.
= 879.6 [M + H]+. C52H66N2O6Zn·2H2O (916.49): calcd. C 68.15, [Cu2L2]: To a solution of ligand 4 (129.4 mg, 0.2 mmol) dissolved
H 7.70, N 3.06; found C 68.18, H 7.44, N 3.00. 1H NMR ([D6]- in thf (5 mL) was added a thf solution (5 mL) of 2 (21.6 mg,
DMSO): δ = 0.85 (t, 1J = 6.5 Hz, 6 H, CH3), 1.20–1.42 (m, 32 H, 0.1 mmol). After the solution turned reddish brown, a methanol/
-CH2-), 1.48–1.56 (m, 4 H, -CH2-), 1.75–1.83 (m, 4 H, -CH2-), 4.20 thf solution (1:3, 8 mL) of anhydrous copper(II) acetate (40.0 mg,
(t, 1J = 6.0 Hz, 4 H, -CH2O-), 6.92 (d, 1J = 9.1 Hz, 2 H, ArH), 0.22 mmol) was added dropwise. After 11 h the mixture gave a pre-
6.99 (s, 2 H, ArH), 7.03 (d, 1J = 8.9 Hz, 2 H, ArH), 7.56 (s, 2 H, cipitate, which was collected by filtration and washed with meth-
ArH), 7.59 (d, 1J = 9.3 Hz, 2 H, ArH), 8.29 (d, 1J = 9.3 Hz, 2 H, anol. Dark-purple crystalline solid. Yield: 137.5 mg (86 %). IR
ArH), 9.23 (s, 2 H, -CH=N-), 9.58 (s, 2 H, ArOH) ppm. (KBr): ν̃ = 3378 (νO–H), 1605 (νC=N), 571 (νM–O), 421 (νM–N) cm–1.
MS (FAB+): m/z = 1596.9 [M + H]+. C94H124Cu2N4O10·2H2O
[CuL1]: To a solution of H2L1 (40.9 mg, 0.05 mmol) dissolved in
(1633.10): calcd. C 69.13, H 7.90, N 3.43; found C 68.92, H 7.81,
thf (2 mL) was dropwise added a methanol solution (2 mL) of an-
N 3.35.
hydrous copper(II) acetate (10.0 mg, 0.055 mmol). An additional
amount of methanol (1 mL) was added, and the mixture was al- [Ni2L2]: To a solution of ligand 4 (129.4 mg, 0.2 mmol) dissolved
lowed to stand for 16 h, by which time a solid had precipitated. in thf (5 mL) was added a thf solution (5 mL) of 2 (21.6 mg,
The product was obtained as a dark-purple crystalline solid. Yield: 0.1 mmol). After the solution turned reddish brown, a methanol
45 mg (100 %). IR (KBr): ν̃ = 3352 (νO–H), 1605 (νC=N), 569 solution (5 mL) of nickel(II) acetate tetrahydrate (54.7 mg,
(νM–O), 419 (νM–N) cm–1. MS (FAB+): m/z = 878.5 [M + H]+, 900.7 0.22 mmol) was added dropwise. After 12 h the mixture gave a pre-
[M + Na]+. C52H66CuN2O6·H2O (896.63): calcd. C 69.65, H 7.64, cipitate, which was collected by filtration and washed with meth-
N 3.12; found C 69.38, H 7.64, N 3.15. anol. Reddish purple crystalline solid. Yield: 132.2 mg (83 %). IR
(KBr): ν̃ = 3354 (νO–H), 1603 (νC=N), 550 (νM–O), 424 (νM–N) cm–1.
[NiL1]: To a solution of H2L1 (40.9 mg, 0.05 mmol) dissolved in thf MS (FAB+): m/z = 1585.4 [M + H]+. C94H124N4Ni2O10·3H2O
(5 mL) was dropwise added a methanol solution (1 mL) of (1641.40): calcd. C 68.78, H 7.98, N 3.41; found C 69.15, H 7.79,
nickel(II) acetate tetrahydrate (13.7 mg, 0.055 mmol). The product N 3.41.
immediately precipitated as a purple crystalline solid. Yield: 41 mg
(94 %). IR (KBr): ν̃ = 3354 (νO–H), 1605 (νC=N), 581 (νM–O), 421 [Fe2L2Cl2]: To a solution of ligand 4 (64.7 mg, 0.1 mmol) dissolved
(νM–N) cm–1. MS (FAB+): m/z = 873.7 [M + H]+, 895.7 [M + in thf (3 mL) was added a thf solution (4 mL) of 2 (10.8 mg,
Na]+. C52H66N2NiO6·H2O (891.77): calcd. C 70.03, H 7.69, N 3.14; 0.05 mmol). After the solution turned reddish brown, a methanol
found C 69.85, H 7.54, N 3.16. 1H NMR ([D6]DMSO): δ = 0.84 solution (2 mL) of iron(III) chloride hexahydrate (29.7 mg,
(t, 1J = 6.3 Hz, 6 H, CH3), 1.20–1.40 (m, 32 H, -CH2-), 1.45–1.54 0.11 mmol) was added dropwise. Triethylamine (10 µL) was added,
(m, 4 H, -CH2-), 1.73–1.80 (m, 4 H, -CH2-), 4.18 (t, 1J = 6.8 Hz, 4 and the mixture was allowed to stand for 16 h. The resulting pre-
H, -CH2O-), 7.04 (d, 1J = 9.1 Hz, 2 H, ArH), 7.08 (s, 2 H, ArH), cipitate was collected by filtration and washed with methanol.
7.10 (d, 1J = 8.9 Hz, 2 H, ArH), 7.64 (d, 1J = 9.2 Hz, 2 H, ArH), Black crystalline solid. Yield: 33.0 mg (40 %). IR (KBr): ν̃ = 3414
7.80 (s, 2 H, ArH), 8.38 (d, 1J = 8.5 Hz, 2 H, ArH), 9.06 (s, 2 H, (νO–H), 1599 (νC=N), 573 (νM–O), 417 (νM–N) cm–1. MS (FAB+): m/z
-CH=N-), 9.44 (s, 2 H, ArOH) ppm. = 1580.7 [M – 2Cl]+. C94H124Cl2Fe2N4O10·2H2O (1688.60): calcd.
C 66.86, H 7.64, N 3.32; found C 66.70, H 7.09, N 3.45.
[FeL1Cl]: To a solution of H2L1 (40.9 mg, 0.05 mmol) dissolved in
thf (2 mL) was dropwise added a methanol solution (1 mL) of
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FULL PAPER H. Houjou, T. Motoyama, K. Araki

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Published Online: December 29, 2008

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