Synthesis, spectroscopy, and electrochemistry of copper(II) complexes with N,N′-bis(3,5-di-t-butylsalicylideneimine) polymethylenediamine ligands

Article abstract of DOI:10.1016/j.saa.2004.03.037

Bulky salen CuL_x derived from aliphatic polymethylene diamines, H₂N-(CH₂)_x-NH₂, where n = 2-6, and 3,5-di-t-butylsalicylaldehyde (H₂L_x) and some corresponding tetrahydrosalan complexes (CuL′_x) have been synthesized and characterized by their IR, UV - vis absorption and EPR spectra, by magnetic moments and by cyclic voltammetry in acetonitrile (for H ₂L_x) and DMF (for CuL_x). Complexes CuL _x and CuL′_x are magnetically normal (μ_exp = 1.83-1.91 μ_B). EPR spectra CuL_x characterized by the axial g and A_Cu, tensors with g∥ > g⊥ and without ¹⁴N-shf resolution in CHCl₃/toluene at 300 and 150K. The CV studies on acetonitrile solutions of H₂L _x revealed a well-defined quasi-reversible redox wave at E _1/2 = 0.95-1.15 V versus Ag/AgCl but CV of the CuL_x complexes in DMF exhibit weak pronounced irreversible oxidation waves at E _pa¹, = 0.51 - 0.98 V and Ep_a¹ = 1.16 - 1.33 V attributable to metal centered Cu(II/III) and ligand centered CuL _x/CuL_x⁺ couples, respectively. A poorly defined wave was observed for the quasi-reversible reduction Cu(II)/Cu(I) at potentials less than - 1.0 V.

Full text of DOI:10.1016/j.saa.2004.03.037

Spectrochimica Acta Part A 61 (2005) 225–231
Synthesis, spectroscopy, and electrochemistry of copper(II)
complexes with N,Nꢀ-bis(3,5-di-t-butylsalicylideneimine)
polymethylenediamine ligands
Veil T. Kasumova,∗, Fevzi Köksalb
a
Chemistry Department of Faculty of Arts and Sciences, Harran University, Sanhurfa 63300, Turkey
Physics Department of Faculty of Arts and Sciences, Ondokuz Mayıs University, Samsun, Turkey
b
Received 10 February 2004; accepted 29 March 2004
Abstract
Bulky salen CuLx derived from aliphatic polymethylene diamines, H2N–(CH2)x–NH2, where n = 2–6, and 3,5-di-t-butylsalicylaldehyde
(H2Lx) and some corresponding tetrahydrosalan complexes (CuLꢀx) have been synthesized and characterized by their IR, UV–vis absorption
and EPR spectra, by magnetic moments and by cyclic voltammetry in acetonitrile (for H2Lx) and DMF (for CuLx). Complexes CuLx and
CuLꢀx are magnetically normal (µexp = 1.83–1.91 µB). EPR spectra CuLx characterized by the axial g and ACu tensors with g|| > g⊥ and
without 14N-shf resolution in CHCl3/toluene at 300 and 150 K. The CV studies on acetonitrile solutions of H2Lx revealed a well-defined
quasi-reversible redox wave at E1/2 = 0.95–1.15 V versus Ag/AgCl but CV of the CuLx complexes in DMF exhibit weak pronounced
irreversible oxidation waves at Ep1a = 0.51 − 0.98 V and Ep2a = 1.16 − 1.33 V attributable to metal centered Cu(II/III) and ligand centered
+
•
CuLx/CuLx couples, respectively. A poorly defined wave was observed for the quasi-reversible reduction Cu(II)/Cu(I) at potentials less
than −1.0 V.
© 2004 Elsevier B.V. All rights reserved.
Keywords: Bulky polymethylene-salen Cu(II) complexes; Spectroscopy; Electrochemistry
1. Introduction
for design of a various homo- or heterodinuclear complexes
[9]. In recent years there has been considerable and grow-
ing interest in the coordination chemistry of main groups
and transition metal complexes with bulky di-t-butylate
salen class ligands prepared from ethylene, cyclohexylene,
and aromatic diamines [2,10,11d]. But transition metal
complexes with bulky salen ligands derived from poly-
methylene diamines, H2N–(CH2)xNH2, n = 3–12 and
3,5-di-t-butylsalicylaldehyde have not yet been extensively
studied.
As a part of our interest on the stereochemistry and
reactivity of redox-active bulky di-t-butyl functional-
ized ligand complexes [11], we report here on the
synthesis, spectral and electrochemical behaviors of a
new series of Cu(II) complexes, CuLx, with tetraden-
tate N,Nꢀ-polymethylene-bis(3,5-di-t-butylsalicylidene) di-
imine ligands (H2Lx), as well as some CuLꢀx chelates,
prepared from their tetrahydrogenated analogs H2Lxꢀ
(Scheme 1).
The coordination chemistry of salen type quadridentate
salicylaldimine ligands with transition metal complexes
has been extensively studied [1] and some of these com-
plexes already have some interesting applications, e.g. in
catalytic oxidation reactions and electrochemical reduc-
tion processes [2], in metalloenzyme-mediated catalysis
[3,4] and asymmetric catalysis [2a-d], metal-containing
liquid–crystalline polymers [5], as catalytically active ma-
terials to develop surface-modified electrodes [6,7]. The
Msalen type chelates have attracted considerable interest
due to their ability to bind reversibly O2 and CO2 [1,3,8],
and because of that they can be used as “metalloligands”
∗
Corresponding author. Tel.: +90-414-312-8456;
fax: +90-414-314-6984.
E-mail address: vkasumov@harran.edu.tr (V.T. Kasumov).
1386-1425/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2004.03.037

226
V.T. Kasumov, F. Köksal / Spectrochimica Acta Part A 61 (2005) 225–231
Scheme 1.
2. Experimental section
2.2. Materials
2.1. Measurements
All chemicals and solvents were reagent grade and
were used without further purification. Cu(AcO)2·H2O,
2,4-di-tert-butylphenol, all diamines, NH2–(CH2)n–NH2,
where n = 2–6, were obtained from Aldrich Chemical
Co. The reagent 3,5-di-t-butylsalicylaldehyde was pre-
pared from commercially available 2,4-di-tert-butylphenol
according to the literature [13].
Elemental analyses (C, H, N) were performed at the Uni-
versity of Fırat Department of Chemistry Microanalytical
Service and were satisfactory for all compounds. Elec-
tronic spectra were measured on a Shimadzu 1601 UV–vis
spectrophotometer. Room temperature solid-state mag-
netic susceptibilities were measured by using a Sherwood
Scientific magnetic susceptibility balance. The effective
magnetic moment, µeff, per copper atom was calculated
from the expression µeff = 2.83(χM · T)1/2 B.M., where
χM is the molar susceptibility corrected using Pascal’s
constants [12] for diamagnetism for all the atoms in the
compounds. IR spectra were recorded as KBr pellets on a
Perkin–Elmer FT-IR spectrophotometer. The ESR spectra
were recorded on a Varian model E 109 C spectrometer in
X-band with 100 kHz modulation frequencies. The g-value
was determined by comparison with a diphenylpicrylhy-
drazyl (DPPH) sample of g = 2.0036. Errors for g- and
A-parameters of the complexes are 0.001 and 0.05 G,
respectively.
Electrochemical measurements were carried out with
a PC-controlled Eco Chemie-Autolab-12 potentiostat/
galvanostat electrochemical analyzer using a three-electrode
cell unit, a platinum working and counter electrodes.
Cyclic voltammetry measurements were obtained in de-
gassed acetonitrile solutions of ca. 10−3 to 10−4 M LxH
and in degassed DMF of ca. 10−3 M CuLx, using 0.04 M
n-Bu4NClO4 and Et4NBF4 as the supporting electrolytes,
respectively, in the potential range +2.0 to −1.5 V. The
measured potentials were recorded with respect to the
Ag/AgCl reference electrode.
2.3. Preparation of ligands and complexes
2.3.1. H2Lx ligands
The tetradentate Schiff base ligands used in this work,
N,Nꢀ-bis(3,5-di-t-butylsalicylidene)-1,2-diaminoethane (H2
L1), N,Nꢀ-bis(3,5-di-t-butylsalicylidene)-1,2-diaminopropane
(H2L2), N,Nꢀ-bis(3,5-di-t-butylsalicylidene)-1,3-diaminopr-
opane (H2L3), N,Nꢀ-bis(3,5-di-t-butylsalicylidene)-1,4-dia-
minobutane (H2L4), N,Nꢀ-bis(3,5-di-t-butylsalicylidene)-1,
5-diaminopentane (H2L5), N,Nꢀ-bis(3,5-di-t-butylsalicylide-
ne)-1,6-diaminohexane (H2L6) were obtained by the con-
densation of 3,5-di-tert-butylsalicylaldehyde and appropri-
ate diamines in methanol. The products were recrystallized
from methanol/CHCl3 (v/v = 5 : 1) and dried in air, yields
92–95%.
2.3.2. CuLx complexes
To a stirring warm solution of H2Lx (0.5 mmol) and
NEt3 (0.14 ml, 1 mmol) in CHCl3 (5 ml) and EtOH (30 ml),
copper(II) acetate monohydrate (0.1 g, 0.5 mmol) in hot
methanol (10 ml) was added. The resulting mixture was
heated at ca. 50–55 ◦C on a water bath with stirring
for about 40–50 min and allowed to cool to room tem-
perature. The CuL1–CuL4 complexes were precipitated

V.T. Kasumov, F. Köksal / Spectrochimica Acta Part A 61 (2005) 225–231
227
Table 1
The melting points, yields and analytical data for H2Lx and CuLx compounds
Compound
Color
T (◦C)
Yield (%)
Elemental analyses (%) (Found/Calc.)
C
H
N
H2L2
H2L3
H2L4
H2L5
H2L6
CuL2
CuL3
CuL4
CuL5
CuL6
Yellow
Yellow
Yellow
Yellow
Yellow
Grey
Green
Green
Dark green
Dark green
158–160
144
154
134
121
>270
>270
>270
>270
95
92
92
94
95
92
88
86
74
68
79.12/78.20
79.24/78.20
79.18/78.42
77.15/78.60
79.42/78.78
70.36/69.75
69.12/69.75
69.78/70.13
71.34/70.49
71.78/70.84
9.86/9.94
9.74/9.94
9.86/10.06
9.78/10.17
9.54/10.28
8.12/8.51
7.88/8.51
8.24/8.65
9.46/8.79
9.59/8.92
6.34/5.53
6.14/5.53
5.78/5.37
4.88/5.24
5.46/5.10
5.26/4.93
4.46/4.93
4.56/4.81
4.38/4.69
4.38/4.59
242–245
immediately as Cu(ac)2·H2O was added to the solution
of H2Lx. The precipitated product was collected by filtra-
tion, washed several times with methanol and recrystal-
lized from methanol/CHCl3 and dried at 60 ◦C for 4–6 h
in air, yields 68–92%. The analytical data are listed in
Table 1.
3.1. IR spectra
The IR spectra of the complexes were interpreted by com-
paring the spectra with that of the free ligands. A medium
intensity broad band at 2500–3100 cm−1 in the spectra of
free ligands, due to ν(OH) of the intramolecularly bonded
N · · · HO, is lack in the spectra of the complexes, indicat-
ing deprotonation of the salicyladehyde moiety of H2Lx. A
strong band observed in the spectra of free H2Lx ligands
in the region of 1629–1634 cm−1 attributable to the azome-
thine group, except CuL1 is shifted to lower wavenumber
(1615–1622 cm−1) in the spectra of CuLx, indicating co-
ordination of the azomethine nitrogen to the copper atom
(Table 2). The spectra of CuL3 and CuL4 unlike analogous
Co(II), Ni(II), Pd(II), Mn(II), VO(II) complexes, display a
doublet bands at 1615 and 1626 cm−1 (for CuL3) and 1615
and 1625 cm−1 (for CuL4), suggesting an inequivalency of
2.3.3. Hydrogenated H2Lxꢀ
Hydrogenated H2Lxꢀ tetrahydrosalan type ligands and their
CuLꢀx complexes were prepared according to previously pub-
lished procedures [11d].
3. Results and discussion
The analytical data of the CuLx complexes indicate 1:1
ligand to metal stoichiometry. Note that our complexes
unlike of their unsubstituted analogs, which were found
to have very low solubility in most coordinating sol-
vents, are well soluble in CHCl3, CH2Cl2, DMF, DMSO
and poorly soluble in solvents such as alcohols, acetoni-
trile and dioxane. Although, transition metal complexes
with L1H2 have previously been reported by us [11d],
for comparative purposes we have included CuL1 to this
paper.
=
the –N CH– group in these complexes. Surprisingly, no
=
lower wavenumber shifts of νN CH in the spectra of CuL1
compared to that in the free H2L1 were observed. Note that
similar unusual behavior of the coordinated –N CH– group
did not occur in the spectra of Co(II), Ni(II), Pd(II), Mn(II),
VO(II) complexes with the same H2L1 ligand [11d]. The
IR spectra of the tetrahydrogenated H2L1ꢀ –H2L4ꢀ ligands ex-
hibit narrow intense bands in the region 3259–3313 cm−1
=
Table 2
IR and electronic spectral data for the H2Lx H4Lxꢀ
Ligand
IR spectra (cm−1
)
Electronic spectra λmax (nm) (log ε, M−1 cm−1
)
=
νCH N
νNH
H2L1
H2L2
H2L3
H2L4
H2L5
H2L6
H2L1ꢀ
H2L2ꢀ
H2L3ꢀ
H2L4ꢀ
1629
1629
1633
1634
1631
1634
–
–
–
–
–
–
–
–
–
–
219 (4.86), 263 (4.82), 330 (4.41), 428 (2.59)
215 (4.86), 235a, 264 (4.22), 328 (3.81), 420 (2.29)
222 (4.85), 262 (4.58), 328 (4.13), 416 (2.61)
218 (4.56), 240a, 264 (4.13), 328 (4.11), 416 (2.82)
219 (4.89), 235 (4.76), 264 (3.89) 331 (3.88) 416 (2.67)
217 (486), 338a, 261 (3.97), 330 (3.97), 416 (2.75)
209 (4.59), 235a, 281 (3.91), 330 (2.23)
3313
3273, 3259
3299
209 (4.66), 223 (4.25), 283 (3.91), 328 (1.98)
209 (4.36), 230a, 282 (3.91), 329
236 (4.71), 284 (3.86), 328 (1.89)
3299
a
Shoulder.

228
V.T. Kasumov, F. Köksal / Spectrochimica Acta Part A 61 (2005) 225–231
Table 3
1H NMR spectral data for the H2Lx (δ, ppm)
=
Compounds
δOH
δCH N
δSal·H
Others
δC(CH3)3
H2L1
H2L2
H2L3
H2L4
H2L6
13.64
13.70
13.80
13.89
13.99
8.38 s, 2H
8.16 s, 1H; 8.37 s, 1H
8.38 s, 2H
8.36 s, 1H
8.34 s, 2H
7.07 d(2.4), 7.36 d(2.4)
7.07 d(2.1), 7.35 d(2.4)
7.07 d(1.72), 7.37 d
7.08 d(2.6), 7.37 d(2.4)
7.07 d(2.2), 7.36 d(2.4)
3.91 t, N–CH2, 4H
1.28 s, 144 s
1.29 s, 1.45 s
1.29 s, 1.45 s
1.30 s, 1.46 s
1.30 s, 1.45 s
3.34 q, CH3, 3.75 m (N–CH–)
3.65 t, N–CH2, 2.15 q, CH2, 2H
3.61 s, 4H, –CH2–, 1.97 s, 4H
3.57 t, 4H, 1.72 m, –CH2–, 8H
due to ν(NH), while they have no bands over the range
1608–1635 cm−1, indicating the absence of the azomethine
group in H2Lxꢀ (Table 2). As can be seen from Table 4
in the IR spectra of hydrogenated CuLꢀx complexes pre-
pared in air, the ν(NH) modes are shifted to lower fre-
quencies (3202–3287 cm−1) and any bands in the region
3.57–3.91 ppm as a triplet pattern. Salicylic protons at 4 and
6 positions appeared as meta-coupled doublets from ring
protons on salicylic moiety at δ 7.05–7.08 ppm (d, 1H, J =
1.72–2.4 Hz) and δ 7.35–7.37 ppm (d, 1H, J = 2.41 Hz).
The spectra of H2Lx contain only two single resonances: at
δ 1.28–1.30 and at δ 1.44–1.46 ppm corresponding to each
of the unique t-Bu groups.
1605–1630 cm−1 attributable to ν(C N) modes have not
=
been observed, indicating that the expected oxidative dehy-
=
drogenation (–CH2–NH– → –CH N–) of hydrogenated lig-
3.3. Electronic spectra
ands in their complexation did not takes place. The low in-
tense bands appeared at ca. 1605 cm−1 in the spectra of H2Lxꢀ
which is assigned to benzene ring stretching vibrations, prac-
tically remaining unchanged in the spectra of CuLꢀx.
Electronic absorption spectral data of H2Lx are very
similar to each other because of their structural identity
(Table 2). Their electronic spectra in ethanol solutions
∗
along with bands assigned to intraligand ␲ → ␲ and
∗
3.2. 1H NMR spectra of H2Lx
n → ␲ transitions, also display the absorption maxima
at 414–428 nm (ε = 310–660 M−1 cm−1) attributable to
∗
The 1H NMR spectral results, obtained for H2Lx in
CDCl3, together with the assignments are presented in
Table 3. All H2Lx tetradentate Schiff bases show a narrow
intense singlet in the region δ 13.64–13.99 ppm assigned to
an n → ␲ transition of dipolar zwitterionic keto-amine
tautomeric structures of H2Lx [14]. The electronic spec-
tra of H2Lꢀ exhibit nearly identical absorptions within the
210–329 nm with the absence of the band at 414–428 nm
detected in the spectra H2Lx.
=
hydrogen bonded salicylic proton. The CH N imine pro-
Electronic spectra of CuLx complexes were recorded in
CHCl3 solution over the range 200–1100 nm (Table 4). The
visible-near-IR spectra of the CuL3–CuL6 complexes con-
sists of a shoulders at 480–500 nm and a maximum or a
broad shoulder around 571–660 nm, which can be assigned
to the dxz,yz → dxy and dx2−y2 → dxy transitions in D2h sym-
metry [15]. The observed trend in the low-energy d–d band
tons except H2L2 exhibit a singlet resonance in the region δ
8.16–8.37 ppm in keeping with their identity. The presence
of a doublet signal at δ 8.16 and 8.37 ppm for the azome-
thine protons in the spectra of H2L2 indicates, as it would
be expected, the nonequivalent nature of the azomethine
protons. Protons of the bridging methylene groups attached
to a nitrogen atom, N–CH2–, resonances in the region δ
Table 4
IR, electronic spectral and magnetic moment data for CuLx and CuLxꢀ
Compound
IR spectra (cm−1
)
µeff (B.M.)
Electronic spectra λmax (nm) (log ε, M−1 l−1
)
=
νC N
νNH
CuL1
CuL2
CuL3
CuL4
CuL5
CuL6
1629
1622
1615
1615
1619
1620
1630
–
–
–
–
–
–
–
1.85
1.83
1.92
1.91
1.82
1.83
1.95
1.56
1.75
2.49
282 (4.47), 384 (4.07), 575 (2.71)
285 (4.79), 383 (4.41), 571 (2.78)
300a, 323 (4.19), 397 (4.11), 480a, 634 (2.42)
317 (4.03), 402 (4.04), 480a, 634 (2.56)
276 (4.59), 327 (4.25), 376 (4.22), 500a (2.69), 660a (2.29)
273 (4.47), 327 (4.13), 377 (4.09), 490a, 660a (2.11)
257 (4.15), 296 (4.29), ∼350a, 416 (3.21), 604 (2.95)
257 (4.14), 298 (4.08), ∼350a, 406 (3.38), 603 (2.86)
256 (4.17), 300 (4.09), ∼350a, 411 (3.13), 611 (2.87)
CuLꢀ1
3249
3215, 3202
3219
b
CuLꢀ2
CuLꢀ3
CuLꢀ4
–
–
3287
a
Shoulder.
All CuLꢀx complexes were prepared under N2.
b

V.T. Kasumov, F. Köksal / Spectrochimica Acta Part A 61 (2005) 225–231
229
maximum shifts to a longer wavelength with increasing of
3.5. EPR spectra
the bridging N–(CH2)x–N chain length (Table 4) is similar
to the trend with stereochemistry observed for their unsub-
stituted analogs [1,16]. The lower-energy ligand-field ab-
sorption of the presented complexes is also red shifted about
10–30 nm compared to those of their non-substituted analogs
in CHCl3 [16]. Thus, the observed red shifts in the d–d band
is affected both by the steric effect of bulky t-Bu groups in
the 3-positions of the salicylaldehyde moieties and increas-
ing of methylene backbone length in CuLx complexes. It is
interesting that the solution spectra of CuLꢀx are very similar
to each other and low energy band at about 603–611 nm is
blue shifted compared to that observed for CuLx.
The spin Hamiltonian parameters of CuLx complexes
are listed in Table 5. The EPR spectra of polycrystalline
samples of CuL1–CuL3 at 300 are very similar and char-
acterized by an axial g tensor with g > g > 2.03 [17]
(Fig. 1a–c). In the solid state spectra of CuL4–CuL6 along
with intense axial doublet spectra of monomeric species, a
weak broad unresolved pattern at g of 2.534, 2.7 and 2.796,
respectively (Fig. 1d–f), attributable to low-field component
||
⊥
of ꢀMs
=
1 transitions typical for copper(II) dimeric
species [18] were also observed. At higher modulation
amplitude for CuL6 complex a very broad weak feature at
ca. g = 5.09 can be detected. The ESR spectra for poly-
crystalline samples of the hydrogenated CuLꢀx (x = 1–4),
at 300 K are similar to each other and characterized by an
axial symmetric g tensor with g > g > 2.03 (Table 4).
3.4. Magnetic moments
The room temperature magnetic moments of CuLx
(Table 4) fall in the range 1.82–1.92 µB which are typical
for square-planar (D4h) and tetrahedrally distorted (D2h)
mononuclear copper(II) complexes with a S = 1/2 spin
state and did not indicate any antiferromagnetic coupling
of spines at this temperature. The relatively higher 1.91
and 1.92 µB values observed for CuL3 and CuL4, seem
to suggest the relatively high tetrahedral distortion from
square-planar geometry for these complexes than others
in polycrystalline state. On the other hand, the µeff data
for CuL1, CuL2, CuL5 and CuL6 fall in the 1.82–1.85 µB
range and are well consistent with a square-planar geometry
(D4h) around the copper centers. The observed moments
probably indicate monomeric compositions, although weak
dimeric interaction cannot be ruled out in the absence of
low-temperature data. The µeff value of 1.95 µB for hy-
drogenated CuLꢀ1 unlike its azomethine CuL1 analogous is
typical for pseudotetrahedral Cu(II) complexes. But µeff
of CuLꢀ2 is lower than that expected for spin-only value
(1.73 µB), probably suggesting the existence of an antiferro-
magnetic interaction between Cu(II) centers. The effective
magnetic moment value of 2.48 µB for orange–brown CuL4ꢀ
complex at 300 K is very close to that which is expected
for two uncoupled S = 1/2 spin centers.
||
⊥
The spin Hamiltonian parameters g , g , A , A , for
||
⊥
||
⊥
CuLx and CuLꢀx in CHCl3 solution are given in Table 4.
ESR spectra of CuLx at 300 K except CuL2 and CuL5 ex-
hibit typical four lined copper(II) signal without any nitro-
gen or proton superhyperfine (shf) splittings on the high
field mI = 1/2 and 3/2 components. The fluid-solution and
frozen glass spectra of CuL2, bearing methyl group on the
ethylene bridge exhibit ill-resolved nine line 14N-shf struc-
ture of 7.6 G (300 K) and well-resolved 15 line shf structure
of 16.3 G (130 K) in the high field wing of the g component
⊥
of the spectra can be attributed to interaction of an unpaired
electron spin with two uneqivalent 14N and hydrogens nu-
clei, which are attached to the carbon atoms adjacent to the
N [17,18]. For CuL5 complex, even in the diluted CHCl3
solution at 300 K, spectral pattern consisting of a broad
component at g = 2.131 and narrow ones at g = 2.052 was
observed (Fig. 1g). It is interesting that upon treatment of this
sample with an excess of (NH4)2[Ce(NO3)6], a one-electron
oxidant, a new spectral pattern with a relatively broad com-
ponent at g1 = 2.212 and a narrow doublets at g2 = 2.113
and g3 = 2.069 spacing of 69 G, as well as a triplet radi-
cal signal centered at g = 2.0036 were observed (Fig. 1h).
ESR spectra of CuLx in CHCl3 at 150 K are characterized
Table 5
ESR parameters for the CuLx and CuLꢀx complexes
Complex
Solid state
Solution spectraa
g
g
giso
Aiso
g
g
A
A
⊥
AN
α2
G
||
⊥
||
⊥
||
CuL1
CuL2
CuL3
CuL4
CuL5
CuL6
CuLꢀ1
CuLꢀ2
CuLꢀ3
CuLꢀ4
2.180
2.176
2.218
2.218
2.212
2.211
2.186
2.175
2.144
2.187
2.039
2.036
2.043
2.056
2.068
2.063
2.049
2.054
2.048
2.051
2.108
2.099
2.154
2.094
2.126
2.134
2.131
2.117
2.082
–
87.5
90
87.5
68
–
80
73.5
72
82
2.156
2.185
2.254
2.224
2.235
2.232
2.363
2.236
2.214
–
2.084
2.056
2.094
2.029
2.072
2.085
2.015
2.057
2.016
–
190
204
192
172
168
167
171.3
190
176
–
36.3
35
43.3
16
–
14
–
12
–
0.725
0.778
0.832
0.722
0.711
0.741
0.853
0.793
0.717
–
4.84
5.15
5.29
4.02
3.19
3.44
3.94
3.03
3.10
3.79
–
36.5
24.7
13
35
–
–
16
–
–
–
a
A value is presented in 10−4 cm−1
.

230
V.T. Kasumov, F. Köksal / Spectrochimica Acta Part A 61 (2005) 225–231
Fig. 1. ESR spectra for powder CuLx at 300 K (a–f); in CHCl3 for CuL5 at 300 K (g); for oxidized CuL5 in CHCl3 at 300 K (h).
by axially symmetric g and A tensors with g > g and
1.256, 1.235, 1.195, 1.088, 1.074 and Epc(V) = 1.054,
1.035, 0.922, 0.919, 0.913 for L1H2 (E1/2 = 1.155 V),
L2H2 (E1/2 = 1.135 V), L3H2 (E1/2 = 1.058 V), L4H2
(E1/2 = 1.004 V) and L5H2 (E1/2 = 0.994 V), respectively.
Under similar conditions L6H2 exhibits ill-defined shoul-
ders at Epa(V) = 0.958 V and Epc = 0.865 V. In the CV
of L2H2 along with irreversible anodic oxidation peak at
Epa = 1.086 V, a quasi-reversible redox couple at potential
||
⊥
A
||
> A (Table 4) without 14N-shf splitting even in di-
⊥
lute solution suggesting that the unpaired electron occupies
a formal dx2−y2 [15,17]. Note that the reason of the absence
of 14N-shfs resolutions in the solution spectra at 300 and
160 K can be related with the distortion of the coplanarity of
the coordination bond due to steric hindrance of t-Bu groups
and the line-broadening effect of protons that can couple
with an unpaired electron and 14N-nuclei [19]. The value
of the in-plane sigma bonding parameter, α2, is estimated
from the expression [15a]: α2 = A /0.036 + (g − ge) +
=
E1/2 = −0.873 V assignable to the reduction of –CH N–
group was also observed.
Due to insolubility of CuLx in acetonitrile we inves-
tigated their redox behaviors in DMF over the potential
range from −1.0 to +2.0 V versus Ag/AgCl. The CV of
these complexes exhibit less pronounced irreversible an-
odic oxidation waves at 0.96, 1.28 V (CuL1), 0.98, 1.33 V
(CuL2), 1.18 V (CuL3), 0.51, 1.16 V (CuL4), 0.69, 1.12 V
(CuL5), which can be attributed to metal centered Cu(II)Lx
→ Cu(III)Lx and ligand centered phenolate/phenoxyl rad-
||
||
3/7(g − ge) + 0.04. As can be seen from Table 4 some
⊥
complexes have the values of α2 in the 0.78–0.85 range,
suggesting that the equatorial bonds are not strong for these
compounds.
4. Electrochemistry
ical [Cu(II)Lx → Cu(II)(Lx +)], oxidations, respectively.
•
For all complexes the high potential wave appeared as a
broad shoulder. The CV of CuL3 and CuL4 complexes
also contain quasi-reversible Cu(II/I) reductive waves at
E1/2 = −0.96 (∆Ep = 0.26 V) and E1/2 = −1.02 V
(∆Ep = 0.28 V), respectively. The irreversibility of the ox-
idation processes probably indicates that the oxidized form
fast undergoes decomposition or reaction by the solvent. It
The cyclic voltammograms (CV) of LxH2 were recorded
at room temperature in acetonitrile in the potential range
−2.0 to 1.75 V at a scan rate of 0.1 V s−1. All ligands show
a single quasi-reversible redox wave at potentials E1/2 rang-
ing from 0.99 to 1.155 V, which can be attributed to the
phenolate/phenoxyl radical couple. Initial anodic scans re-
veal well-defined waves with redox potentials at Epa(V) =

V.T. Kasumov, F. Köksal / Spectrochimica Acta Part A 61 (2005) 225–231
231
[9] (a) S.J. Gruber, C.M. Harris, E. Sinn, J. Inorg. Nucl. Chem. 30
(1968) 1805;
should be noted that the 3-t-Bu-5-Me substituted Cusalen,
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oxidation wave at E1/2 = 0.96 V, in dichloromethane
[20], but its non-substituted Cusalen analogue showed only
a quasi-reversible electrochemical reduction of Cu(II) at
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CuLꢀ1 and CuLꢀ2 complexes exhibit very similar a poorly
defined irreversible anodic oxidation curves at potentials
ca. 0.69, 1.03, and 1.42 V.
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Acknowledgements
The financial support of Harran University Research Fund
(HUBAK) is gratefully acknowledged (Project No.: 233).
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23 (1982) 114;
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