JOURNAL OF COORDINATION CHEMISTRY
3
Mass hunter software for their analysis. Electronic absorption spectra were obtained with a
Shimadzu UV-1601 UV–Vis spectrophotometer at room temperature. Quartz cuvettes of
3
1
cm path length and 3 cm volume were used for all measurements. EPR spectrum of the
1
complex was obtained on an X-band Microwave Unit, JES-FA200 ESR spectrometer. H and
C NMR spectra were recorded on a Varian 400 MHz instrument.
13
2
.2. Synthesis of 2-methoxy-6-(tris(hydroxymethyl)methyliminomethyl)phenol
(
H L)
4
The ligand was prepared by condensation of 3-methoxysalicylaldehyde and tris(hydrox-
ylmethyl)amino methane at room temperature. A methanolic solution (10 mL) of tris(hy-
droxylmethyl)amino methane (10 mmol, 1.21 g) was added dropwise to a methanolic
solution (10 mL) of 3-methoxysalicylaldehyde (10 mmol, 1.52 g) with constant stirring. The
resulting yellow reaction mixture was stirred for 2 h and a yellow compound was separated
out and filtered. The crude product was washed with ethanol and diethyl ether, dried and
collected. The yellow product was re-dissolved in methanol and filtered and the filtrate
kept for crystallization under slow evaporation conditions at room temperature. The crys-
talline material was collected by filtration and dried in air to afford H L as deep yellow solid.
4
Yield: 1.786 g (70%). C H NO (255.27): C, 56.46; H, 6.71; N, 5.48%. Found: C, 56.44; H, 6.68;
1
2
17
5
+
−1
N, 5.50%. HRMS: [M + H] , m/z, 256.118 Calcd: m/z, 255.27 (100%). FTIR (KBr), cm : 414 (vs),
28 (s), 613 (w), 662 (w), 727 (w), 851 (s), 877 (w), 913 (m), 962 (m), 1023 (s), 1072 (s), 1167
5
(
1
s), 1232 (vs), 1300 (s), 1372 (vs), 1414 (vs), 1467 (s), 1545 (vs), 1646 (vs), 1818 (w), 1880 (w),
1
952 (w), 2606 (w), 2832 (w), 2916 (w), 2949 (w), 2988 (w), 3425 (br). H NMR (DMSO-d ,
6
1
4
00 MHz, δ, ppm): 4.907 (s, H, phenolic–OH), 8.456 (s, 1H, imine), 6.944, 6.924 (doublet,
H, Ar), 6.890, 6.871 (doublet, H, Ar), 6.581, 6.563, 6.542 (m, 1H, Ar), 3.611 (s, 6H, CH ), 3.718
s, 3H, OMe), 3.525 (s, 2H, H O). C NMR (DMSO-d , 400 MHz, δ, ppm): 164.266 (−CH=N−),
1
1
2
1
3
(
2
6
1
6
59 (Ar-C-OMe), 149.754 (Ar-C-OH), 124.343 (Ar-C-imine), 114.551-117.174 (Ar-C),
6.520 (-CH2-OH), 61.311 (tertiary carbon), 55.881 (-OCH ). UV–Vis spectra [λ , nm (ε, L
3
max
−
1
−1
4
4
4
mol cm )] (CH OH solution): 202 (8.82 × 10 ), 241 (7.97 × 10 ), 293 (5.78 × 10 ), 420
3
(
2.53 × 104).
2
.3. Synthesis of [Mn(H L) ] (1)
2
2
A methanolic solution (5 mL) of triethylamine (4 mmol, 0.404 g) was added dropwise to a
methanolic solution (10 mL) of H L (2 mmol, 0.510 g) with constant stirring at 27 °C. To this
4
mixture, dropwise addition of methanolic solution (10 mL) of Mn(OAc) ∙4H O (1 mmol,
2
2
0
.245 g) results in a deep brown solution. The whole reaction mixture was stirred for 2 h and
filtered. The filtrate was kept at room temperature. Slow evaporation of the filtrate produces
brown single crystals after a few days. Yield: 0.422 g (75%). Anal. Calcd for C H MnN O
2
4
30
2
10
+
(
561.44): C, 51.29; H, 5.34; N, 4.98%. Found: C, 51.32; H, 5.36; N, 5.33. HRMS: [M + H] , m/z,
−1
5
7
1
62.139 Calcd: m/z, 561.44 (100%). FTIR (KBr), cm : 564 (w), 597 (w), 636 (w), 665 (w), 749 (s),
84 (w), 814 (w), 988 (vs), 1047 (s), 1105 (w), 1137 (w), 1173 (w), 1221 (s), 1251 (vs), 1306 (vs),
374 (w), 1416 (vs), 1467 (s), 1548 (vs), 1623 (w), 2852 (w), 2943 (w), 2985 (w), 3422 (br). UV–Vis
spectra [λ , nm (ε, L mol− cm )] (CH OH solution): 202 (3.33 × 10 ), 276 (4.33 × 10 ), 420
1
−1
5
4
max
3
3
(
6.71 × 10 ).