2
S. Onur et al. / Journal of Molecular Structure 1200 (2020) 127135
metal complexes have been synthesized and characterized using
the micro-analyses, mass spectra, FTIR, UVevis (solution and sol-
vent free), emission-excitation and 1H(13C)NMR spectra. Addition-
ally, electrochemical and thermal properties of the metal free
ligands and their Cu2þ and Pt2þ complexes have viewed. Dyeing
properties of the DB9, ligands and their metal complexes on the
wool have been investigated with/without mordants. Without
mordant in the dyeing process, none of DB9 and other materials
have good dyeing properties on wool.
(CH]N), 159.72e108.15 (AreC), 60.34 (OeCH2), 56.40 (NeCH2).
Mass spectrum (ESI/MS, m/z): Calcd.: 436.46, found: 436.18 [M]þ;
calcd.: 437.46, found: 437.18 [Mþ1]þ; calcd.: 438.47, found: 438.48
[Mþ1]þ; calcd.: 439.48, found: 439.18 [Mþ1]þ. FT-IR: (KBr, cmꢁ1):
3305
n
(-O-H)phenolic, 3219
n
(-O-H)alph, 2965
n(-C-H)alph, 1599 n(-
CH]N-), 1505
n
(-N]N-), 1392
n
(-C-OH)phenolic.
HL5: (C23H24N4O5). Yield: 82%, color: dark brown, melting point:
>250 ꢀC. Elemental analyses, found (calcd. %): C, 63.21 (63.29); H,
5.47 (5.54); N, 12.90 (12.84). 1H NMR (CDCl3,
d
(ppm)): 8.60 (s, 1H,
CH]N), 7.91e6.52 (m, 10H, AreH), 3.94 (t, 2H, OeCH2), 3.68 (t, 2H,
NeCH2). 13C NMR (CDCl3,
(ppm)): 165.83 (CH]N), 157.50e107.45
2. Methods and materials
d
(AreC), 58.12 (OeCH2), 54.30 (NeCH2). Mass spectrum (ESI/MS, m/
z): Calcd.: 437.46, found: 437.24 [Mþ1]þ; calcd.: 410.42, found:
410.17 [C21H22N4O5eC2H2]þ; calcd.: 394.40, found: 394.19
Physical measurements have given in the Supplemantary file. In
addition, dyeing procedure of the wool has also given in the Sup-
plemantary file.
[C21H20N3O5-(NC2H4]þ. FT-IR: (KBr, cmꢁ1): 3300
n
(-O-H)phenolic
,
3175
1443
n
(-O-H)alph, 2878
(-C-OH)phenolic
n
(-C-H)alph, 1610
n
(-CH]N-), 1505 (-N]N-),
n
2.1. Preparation of the azo imine compounds (HL1-HL5)
n
.
The salicylaldehyde derivatives (1 mmol; 152 mg 3-, 4- and 5-
methoxy salicylaldehyde for the ligands HL1-HL3) in methanol
(20 mL, absolute) and the azo amine compound (Disperse Black 9)
(1 mmol, 300 mg) in methanol (20 mL, absolute) were mixed and
refluxed for about two days at 80 ꢀC. The color of the solution
changed to orange. After cooling the solution, the resulting pre-
cipitate was filtered and washed with cold methanol. Single crystals
of the Schiff base compounds (HL1-HL3) suitable for X-ray diffrac-
tion study were obtained by slow evaporation of the compounds in
methanol. Physical properties and other spectroscopic data are
given below.
2.2. Preparation of the Cu(II) and Pt(II) metal complexes
The complexes were prepared according to a known procedure.
The azo imine ligands HL1-HL3 (0.434 g, 1 mmol) were dissolved in
the ethanol (20 mL) solution and the metal salts [1 mmol; 0.171 g
for CuCl2$2H2O; 0.420 g for K2[Pt(Cl)4] were added to the mixture
of CH3OH (20 mL) and the solution was refluxed during 24 h. The
color of the reaction solution changed to the brown or purple. The
mixture was cooled to the room temperature, and the precipitated
complex was filtered by vacuum, washed three times by the
ethanol, and then dried under vacuum desiccator. Purity of the
complexes were checked by t.l.c. studies.
HL1: (C23H24N4O4). Yield: 80%, color: dark orange, melting
point: 205 ꢀC. Elemental analyses, found (calcd. %): C, 65.79 (65.70);
[Cu(L1)Cl(H2O)]3H2O: Yield: 65%, color: Brown, melting point:
>250 ꢀC. Elemental analyses, found (calcd. %): C, 46.22 (46.78); H,
5.18 (5.29); N, 9.44 (9.49). Mass spectrum (ESI/MS, m/z): Calcd.:
554.48, found: 555.24 [MþH2O]þ, calcd.: 555.49, found: 556.24
[MþHþH2O]þ, calcd.: 556.49, found: 557.25 [Mþ2H þ H2O]þ,
calcd.: 510.43, found: 511.24 [C21H23ClCuN4O5eC2H3OH]þ. FT-IR:
H, 5.82 (5.75); N, 13.25 (13.33). 1H NMR (CDCl3,
d
(ppm)): 8.77 (s,
1H, CH]N), 7.80e6.37 (m, 11H, AreH), 3.70 (t, 2H, OeCH2), 3.58 (t,
2H, NeCH2). 13C NMR (CDCl3,
(ppm)): 164.35 (CH]N),
d
155.20e108.70 (AreC), 58.10 (OeCH2), 53.15 (NeCH2). Mass spec-
trum (ESI/MS, m/z): Calcd.: 420.46, found: 421.19 [M]þ; calcd.:
421.46, found: 422.19 [Mþ1]þ. FT-IR: (KBr, cmꢁ1): 3336
n
(-O-
(KBr, cmꢁ1): 3433
), 1514 (-N]N-), 1380 n
n
(eCH2eOH), 2925
(-C-OH).
n(-C-H)alph, 1598 n(-CH]N-
H)phenolic, 3168
(-N]N-), 1435
HL2: (C23H24N4O4). Yield: 83%, color: dark orange, melting
point: 203 ꢀC. Elemental analyses, found (calcd. %): C, 65.77 (65.70);
H, 5.71 (5.75); N, 13.42 (13.33). 1H NMR (CDCl3,
(ppm)): 9.70 (s,
2H, Ph-OH), 8.73 (s, 1H, CH]N), 7.87e6.26 (m, 11H, AreH), 3.78 (t,
2H, OeCH2), 3.67 (t, 2H, NeCH2). 13C NMR (CDCl3,
(ppm)): 165.10
n
(-O-H)alph, 2960
n
(-C-H)alph, 1610
n
(-CH]N-), 1506
n
n
n
(-C-OH)phenolic
.
[Cu(L2)Cl(H2O)]3H2O: Yield: 68%, color: Brown, melting point:
>250 ꢀC. Elemental analyses, found (calcd. %): C, 47.53 (46.78); H,
5.38 (5.29); N, 12.93 (9.49). Mass spectrum (ESI/MS, m/z): Calcd.:
536.47, found: 536.22 [M]þ; calcd.: 537.47, found: 538.29 [Mþ1]þ,
calcd.: 554.48, found: 554.27 [MþH2O]þ; calcd.: 568.50, found:
d
d
568.20 [MCH3OH]þ. FT-IR: (KBr, cmꢁ1): 3434
n(-O-H), 2925
n(-C-
(CH]N), 157.33e108.22 (AreC), 58.40 (OeCH2), 53.15 (NeCH2).
Mass spectrum (ESI/MS, m/z): Calcd.: 420.46, found: 421.19 [M]þ;
calcd.: 421.46, found: 422.19 [Mþ1]þ; calcd.: 419.45, found: 419.27
H)alph, 1598 n(-CH]N-), 1515 n(-N]N-), 1386 n(-C-O).
[Cu(L3)Cl(H2O)]3H2O: Yield: 62%, color: Brown, melting point:
>250 ꢀC. Elemental analyses, found (calcd. %): C, 46.52 (46.78); H,
5.69 (5.29); N, 9.93 (9.49). Mass spectrum (ESI/MS, m/z): Calcd.:
553.47, found: 553.24 [M-1]þ; calcd.: 554.48, found: 554.45
[Mþ1]þ, calcd.: 585.51, found: 584.49 [MþH2OþCH3OHþ1]þ. FT-IR:
[M-1]þ. FT-IR: (KBr, cmꢁ1): 3225
n
(-O-H)phenolic, 3150
n
(-O-H)alph
,
2955
n
(-C-H)alph, 1613
n
(-CH]N-), 1508 (-N]N-), 1460 n
n
(-C-
OH)phenolic
.
HL3: (C23H24N4O4). Yield: 85%, color: orange, melting point:
(KBr, cmꢁ1): 3433
(-N]N-), 134 (-C-O).
n(-O-H), 2925 n(-C-H)alph, 1599 n(-CH]N-), 1513
202 ꢀC. Elemental analyses, found (calcd. %): C, 65.76 (65.70); H,
n
n
5.68 (5.75); N, 13.41 (13.33). 1H NMR (CDCl3,
d
(ppm)): 8.78 (s, 1H,
CH]N), 7.88e6.82 (m, 11H, AreH), 3.79 (t, 2H, OeCH2), 3.67 (t, 2H,
NeCH2). 13C NMR (CDCl3,
(ppm)): 165.04 (CH]N), 155.50e108.65
[Cu2(L4)Cl(H2O)2]: Yield: 60%, color: Brown, melting point:
>250 ꢀC. Elemental analyses, found (calcd. %): C, 44.89 (43.71); H,
3.71 (3.99); N, 9.46 (8.86). Mass spectrum (ESI/MS, m/z): Calcd.:
633.01, found: 633.23 [Mþ1]þ; calcd.: 652.04, found: 652.25
d
(AreC), 60.45 (OeCH2), 55.00 (NeCH2). Mass spectrum (ESI/MS, m/
z): Calcd.: 420.46, found: 421.20 [M]þ; calcd.: 421.46, found: 422.20
[Mþ1]þ; calcd.: 419.45, found: 419.25 [M-1]þ. FT-IR: (KBr, cmꢁ1):
[MþH2Oþ1]þ. FT-IR: (KBr, cmꢁ1): 3435
n
(-O-H), 2925
n(-C-H)alph,
1630 n(-CH]N-), 1506 n(-N]N-), 1429 n(-C-OH).
3250
n
(-O-H)phenolic, 3074
n
(-O-H)alph, 2891
n
(-C-H)alph, 1627
n
(-
[Cu2(L5)Cl(H2O)3]: Yield: 63%, color: Brown, melting point:
>250 ꢀC. Elemental analyses, found (calcd. %): C, 42.58 (42.50); H,
4.27 (4.19); N, 8.70 (8.62). Mass spectrum (ESI/MS, m/z): Calcd.:
589.97, found: 590.64 [M-C2H2O]þ; calcd.: 605.97, found: 605.39
[M-C2H2]þ; calcd.: 633.01, found: 633.12 [Mþ1]þ. FT-IR: (KBr,
CH]N-), 1514
n
(-N]N-), 1467 n(-C-OH)phenolic.
HL4: (C23H24N4O5). Yield: 88%, color: dark orange, melting
point: 221 ꢀC. Elemental analyses, found (calcd. %): C, 63.37 (63.29);
H, 5.60 (5.54); N, 12.77 (12.84). 1H NMR (CDCl3,
d
(ppm)): 11.80 (s,
3H, Ph-OH), 8.62 (s, 1H, CH]N), 7.95e6.48 (m, 10H, AreH), 3.75 (t,
2H, OeCH2), 3.36 (t, 2H, NeCH2). 13C NMR (CDCl3,
(ppm)): 165.20
cmꢁ1): 3440
n
(-O-H), 2971
n(-C-H)alph, 1631 n(-CH]N-), 1505 n(-
d
N]N-), 1310 n(-C-OH).