Copper(II) complexes with ZnO nanoparticles thin layers
Philips (Almelo, The Netherlands) XPERT θ–2θ 2.3 Synthesis of the Cu(II) complexes
diffractometer with CuKα radiation. The indentation
properties of the layers were made on NHT2 microin- 2.3a [Cu(en(pyca)2)Cl2] (1a): Ethanolic solution of
dentation tester (TTX-NHT) from Anton Paar TriTec CuCl2 x 2H2O (0.0287 g, 0.16 mmol in 40 mL ethanol)
SA with a Berkovich indenter using loads 20 and was added to en(pyca)2 (1) (0.0396 g (0.16 mmol) in
100 mN and holding time of 5 s. The system hard- EtOH. The reaction mixture was stirred at 25◦C for
ness and elastic modulus were determined from the 4 h, then, the solvent was removed under reduced
indentation curves by the standard Oliver and Pharr pressure and a dark green solid was isolated.
[Cu(en(pyca)2)Cl2] (1a) (Yield 72.8%) Analysis: Cal-
culated for C14H14N4Cl2Cu: Cu 17.04, C 45.11, H
3.78, N 15.03. Found: Cu 16.61, C 45.48, H 4.11, N
15.34 [%]. IR (KBr, cm−1): 3386 m ν(N-H), 3068 m
ν(C=CH), 2922m ν(C-H), 1604vs ν(C=N), 1569m
ν(C-N), 1447s ν(C=C), 303s ν(Cu-Cl), 422s ν(Cu-
N).37 UV-visible in MeCN [λmax/nm (ε/[dm3· mol−1·
cm−1])] 255(8461), 320(2307).
2.2 Synthesis
2.2a Synthesis of en(pyca)2 (1): Ethylenediamine
(en) (60 μL, 1 mmol) in EtOH was added to pyridine-
2-carboxaldehyde (pyca) (190 μL, 2 mmol). The mix-
ture was stirred under reflux for 2 h. The orange
precipitate formed was recrystallized from ethanol.
In the same way [Cu(en(pyca)2)(OOCCH3)2] (1b),
[Cu(en(4Him)2)Cl2] (2a) and [Cu(en(dmbaH)2)Cl2]
(3a) were synthesized (figure 1).
1
(82.7% yield). H NMR [ppm]: δ 8.62 (d, 2H, arom.),
8.42 (s, 2H, CH=N), 7.98 (d, 2H, arom.), 7.73 (2H,
arom.), 7.30 (ddd, 2H, arom.), 4.07 (s, 4H, -CH2-).
13C NMR [ppm]: δ 163.4 C2, 154.4 C3, 149.4 C7,
136.5 C5, 124.7 C6, 121.3 C4, 61.3 C1(CH2). 15N
NMR [ppm]: -42.5 N(1), -67.3 CH=N. IR (KBr,
cm−1): 3010-3070s ν(C-HAr), 2922, 2853s ν(CH),
1645m ν(C=N), 1584s ν(C-N), 1434m ν(C=C).6,35–40
(vs, very strong; s, strong; m, medium; w, weak, vw
2.3b [Cu(en(pyca)2)(OOCCH3)2] (1b): (79.2% yield,
0.03194 g 0.16 mmol Cu(OOCCH3)2 x H2O, 0.0396 g
0.16 mmol en(pyca)2). Analysis: Calculated for
C18H20N4O4Cu: Cu 15.13, C 51.48, H 4.80, N 13.34;
Found: Cu 15.19, C 51.68, H 4.29, N 13.04 [%]. IR
(KBr, cm−1): 3422m ν(OH), 3074w ν(C=CH), 1598vs
ν(C=N), 1547vw ν(C-N), 1444m ν(C=C), 1710s
UV-visible in MeCN [λmax/nm(ε/[dm3·mol−1· cm−1])]
−
−
νasCOO , 1476m νsCOO , 1292m ν(C-O), 92w4 δ(O-H),
550m ν(Cu-O), 454m ν(Cu-N).6,7,36,37,44 UV-visible in
MeCN [λmax/nm (ε/[dm3·mol−1·cm−1])] 210(37795),
235(37520), 267(38120), 319(25326).
2.2b Synthesis of en(4Him)2 (2): (92.1% yield, 252(6299), 326(1574).
(60 μL, 1 mmol en, 0.1922 g, 2 mmol 4Him). 13C CP
MAS NMR [ppm]: δ 156.1 C2, 139.4 C5, 128.6 C3,
123.6 C4, 62.2 C1(CH2). IR (KBr, cm−1): 3436w
ν(N-H), 2913–3032w ν(-CH), 1648vs ν(C=N), 1512s
ν(C-N), 1450vs, 1472m ν(C=C).6,35–37,41 UV-visible in
MeCN [λmax/nm (ε/[dm3· mol−1· cm−1])] 273(31520),
2.3c [Cu(en(4Him)2)Cl2] (2a): (84.50% yield,
CuCl2 x 2H2O 0.0287 g, 0.16 mmol, 0.03459 g,
0.16 mmol en(4Him)2). Analysis: Calculated for
C10H12N6Cl2Cu: Cu 18.12, C 34.24, H 3.44, N 23.96;
Found: Cu 18.13, C 34.48, H 3.12, N 23.71 [%]. IR
(KBr, cm−1): 3422m ν(N-H), 2931w, 2853m ν(CH),
1635vs ν(C=N), 1508w ν(C-N), 1438s ν(C=C),
313m ν(Cu-Cl), 458 w ν(Cu-N).42,45 UV-visible in
MeCN [λmax/nm (ε/[dm3· mol−1· cm−1])] 264(9122),
322(1403).
2.2c Synthesis of en(dmbaH)2 (3): yield (92.2%,
1
60 μL, 1 mmol en, 0.3323 g, 2 mmol 4Him. H NMR
[ppm]: δ 8.71 (s, 2H, CH=N), 7.51 (d, 2H), 6.95
(dd, 2H), 6.85 (d, 2H), 3.99 (s, 4H, -CH2-), 3.82
(s, 6H) 3.79 (s, 6H) 13C NMR [ppm]: δ 158.6 C2,
153.8 C5, 153.4 (C8), 125.3 C3, 118.6 C6, 112.7 2.3d [Cu(en(dmbaH)2)Cl2] (3a): (76.4% yield,
C7, 110.6 C4, 61.9 C1(CH2), 56.3 C10(OCH3), 55.8 CuCl2 x 2H2O 0.0287 g, 0.16 mmol, 0.05702 g,
C9(OCH3). 15N NMR [ppm]: -69.6 -CH=N. IR (KBr, 0.16 mmol en(dmbaH)2). Analysis: Calculated for
cm−1): 3309 vs ν(N-H), 3009–3064m ν(C-HAr), 2906, C20H24N2O4Cl2Cu: Cu 12.94, C 48.93, H 3.92, N 5.70;
2831s ν(CH), 1637vs ν(C=N), 1582s ν(C-N), 1427s, Found: Cu 13.36, C 48.64, H 4.02, N 5.39 [%]. IR (KBr,
1496s ν(C=C), 1303s ν(Ph-O).36,37,42,43 UV-visible in cm−1): 3307vs ν(N-H), 3009-3064vs ν(C-HAr), 2953,
MeCN [λmax/nm (ε/[dm3·mol−1·cm−1])] 222(49732), 2967vs ν(CH), 1654vs ν(C=N), 1587vs ν(C-N), 1453s,
251(29946), 332(15508) (figure 1).
1496s ν(C=C), 477w ν(Cu-N), 373s ν(Cu-Cl).6,34