Dalton Transactions
Page 10 of 14
Dalton Transactions
DOI: 10.1039/C5DT02211H
the terpy moiety on the biological properties of new copper(II) MHz, d6ꢀDMSO):
δ
(ppm) = 166.2 (Ce’’), 156.8 (Ce’), 154.8
complexes derived from
2
.
(Cd’), 149.3 (Ca), 137.4 (Cc), 133.9 (Ck’), 132.8 (Cf’), 132.6
(Ch’), 128.1 (Ch), 127.9 (Cg), 126.4 (Cf), 126.2 (Cb), 125.5 (Ci),
124.6 (Cj), 120.9 (Cd), 107.2 (Ce), 69.6 (Ck). IR (KBr):
3426, 1583, 1561, 1404, 1196, 1022, 796 cm–1.
ν =
Experimental section
General methods
Synthesis of 4'ꢀ((1Hꢀbenzo[d]imidazolꢀ2ꢀyl)methoxy)ꢀ2,2':6',2''ꢀ
terpyridine (bimztpy : 0.250 g (1.67 mmol) of benzimidazolꢀ2ꢀ
All reactions were performed under aerobic conditions and all
reagents and solvents were purchased from SigmaꢀAldrich or
Acros Organics. The reference copper(II)ꢀphenanthroline
complex [Cu(H2O)(1,10ꢀphenanthroline)2](NO3)2 was prepared
)
methanol was added to a suspension of KOH (0.470 g; 8.38
mmol) in 12 mL of dry DMSO. After stirring for 30 minutes at
70 ºC, 0.452 g (1.68 mmol) of Cltpy was added, and the
resulting reaction mixture was further stirred for 4 hours at 70
ºC. Subsequently, this reaction mixture was poured onto 150
mL of ice water. The white precipitate formed was filtered off,
washed with cold water and dried. Yield = 0.259 g (0.68 mmol,
41%). Anal. Calcd for [bimztpy + 2 H2O], C23H21N5O3: C,
66.50; H, 5.09; N, 16.85. Found: C, 65.52; H, 5.23; N, 16.99.
following the procedure described by K. J. Catalan et al 69
.
pBR322 plasmid DNA was purchased from Roche and calf
1
thymus DNA was obtained from SigmaꢀAldrich. H, 13C {1H}
and heteronuclear {1H–13C}ꢀHSQC NMR spectra were
recorded at room temperature with a Varian Unity 400 MHz
spectrometer. Proton and carbon chemical shifts are expressed
in parts per million (ppm,
δ scale) and are referenced to the
ESIꢀMS: m/z = 781.28 [2M + Na]+, 402.13 [M + Na]+, 380.15
peak of the solvent used. Infrared spectra (as KBr pellets) were
recorded using a Nicoletꢀ5700 FTꢀIR (in the range 4000–400
1
[M + H]+. H NMR (400 MHz, d6ꢀDMSO):
2H,
δ
(ppm) = 8.73 (d,
= 7.9 Hz, Hd), 8.14 (s, 2H,
= 7.7 Hz, Hc), 7.57 (m, 2H, Hf), 7.51 (dd,
= 7.7 Hz, Hb), 7.20 (dd, 2H, = 5.9 Hz
= 3.1 Hz, Hg), 5.64 (s, 2H, Hk). 13C NMR (400 MHz, d6ꢀ
(ppm) = 166.3 (Ce’’), 157.0 (Ce’), 154.9 (Cd’), 149.6
(Ck’), 149.5 (Ca), 137.7 (Cf’), 137.6 (Cc), 124.8 (Cb), 124.8 (Cf),
−
1
J = 4.3 Hz, Ha), 8.62 (d, 2H, J
cm ), and data are represented as the frequency of absorption
−
1
He), 8.01 (dd, 2H,
J
(cm ). Elemental analyses were performed by the Servei de
Microanalisi, Serveis Cientificotècnics of the University of
Barcelona. UVꢀVis experiments were performed with a Varian
Caryꢀ100 spectrophotometer. The fluorescence measurements
2H,
and
J
J
= 4.3 Hz and
J
J
DMSO):
δ
were carried out with
spectrofluorometer. ESI Mass Spectroscopy was carried out
using LC/MSDꢀTOF Spectrometer from Agilent
a
KONTRON SFM 25
122.3 (Cg), 121.3 (Cd), 107.4 (Ce), 64.2 (Ck). IR (KBr):
3187, 1583, 1565, 1348, 739 cm–1.
ν =
a
Technologies, equipped with electrospray ionization (ESI)
source at the Serveis Cientificotècnics of the University of
Barcelona.
Preparation of the copper(II) complexes
0.41 mmol of the ligand were suspended in 40 mL of methanol
and heated at 50 ºC until complete dissolution. To this solution,
0.100 g (0.41 mmol) of copper(II) nitrate trihydrate in 10 mL of
methanol were added. The resulting mixture was stirred at 40
ºC for 2 hours and then left for the slow evaporation of the
solvent. After a few days, a precipitate or crystals appeared,
which were filtered off, washed with ethyl ether and dried
under reduced pressure.
Preparation of the ligands naphtpy and bimztpy
The ligands were synthesized by reaction of 2ꢀ
naphthalenemethanol or benzimidazolꢀ2ꢀmethanol with 4'ꢀ
chloroꢀ2,2':6',2''ꢀterpyridine (Cltpy) in DMSO in the presence
of potassium hydroxide, following a known procedure.48
[Cu(Cltpy)(H2O)(NO3)2] (
for C15H12ClCuN5O7 (%): C, 38.07; H, 2.56; N, 14.80. Found:
C, 37.94; H, 2.61, N, 14.77. IR (KBr): = 3414, 3098, 1585,
1561, 1445, 1416, 1404, 1274, 1112, 1017, 802 cm–1.
[Cu(H2O naphtpy)(NO3)](NO3) ( : Yield: 192 mg [79%].
Anal. Calcd for C26H21CuN5O8 (%): C, 52.48; H, 3.56; N,
1): Yield: 98 mg [51%]. Anal. Calcd
Synthesis
terpyridine
of
4'ꢀ((naphthalenꢀ2ꢀyl)methoxy)ꢀ2,2':6',2''ꢀ
0.100 (0.632 mmol) of 2ꢀ
(
naphtpy
)
:
g
ν
naphthalenemethanol was added to a suspension of KOH
(0.039 g; 0.700 mmol) in 15 mL of dry DMSO. After stirring
for 30 minutes at 70 ºC, 0.165 g (0.620 mmol) of Cltpy was
added, and the resulting reaction mixture was further stirred for
4 hours at 70 ºC. Subsequently, this reaction mixture was
poured onto 150 mL of ice water. The white precipitate formed
was filtered off, washed with cold water and chloroform (3 × 5
mL), and dried under reduced pressure. Yield = 0.199 g (0.512
mmol, 81%). Anal. Calcd for [naphtpy + 0.35 DMSO],
C26.7H21.1N3SO1.35: C, 77.10; H, 4.89; N, 9.76. Found: C. 76.94;
)
(
2)
11.77. Found: C, 52.46; H, 3.19, N, 11.79. IR (KBr):
3061, 1617, 1474, 1383, 1222 cm–1.
ν = 3493,
[Cu(bimztpy)(H2O)(NO3)](NO3) (3): Yield: 204 mg [81%].
Anal. Calcd for {[Cu(bimztpy)(H2O)(NO3)](NO3) + 1.5 H2O}
C23H23CuN7O9.5 (%): C, 45.06; H, 3.78; N, 15.99. Found: C,
45.11; H, 3.10, N, 15.88. IR (KBr):
1383, 1217 cm–1.
ν = 3422, 3074, 1617, 1478,
H, 5.10; N, 10.08. ESIꢀMS: m/z = 390.23 [M + H]+, 141.07 [(2ꢀ
methyl)naphthalene ꢀ H]+. H NMR (400 MHz, d6ꢀDMSO):
1
δ
X-ray crystallography
(ppm) = 8.72 (d, 2H,
J = 4.0 Hz, Ha), 8.62 (d, 2H, J = 8.0 Hz,
Data for the ligand Naphtpy were collected on colourless plate
of dimensions 0.28 × 0.08 × 0.02 mm3 at 100 K using a Bruker
APEX II QUAZAR diffractometer equipped with a microfocus
Hd), 8.12 (s, 2H, He), 8.08 (s, 1H, Hf), 8.01 (m, 2H, Hc), 7.99
(m, 1H, Hh), 7.96 (m, 1H, Hg), 7.67 (d, 2H, J = 4.0 Hz, Hi), 7.54
(m, 2H, Hb), 7.49 (m, 2H, Hj), 5.58 (s, 2H, Hk). 13C NMR (400
multilayer monochromator with Mo Kα radiation (λ = 0.71073
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Dalton Trans., 2015, 44, 1-10 | 9