J. Zhou et al. / Journal of Molecular Structure 1058 (2014) 14–21
17
2.4.4. Synthesis of 3-bromo-6-(1,10-phenanthroline-[5,6-b]imidazole-
2-yl)carbzole [21](5) BPIK
2.4.10. Synthesis of polymeric metal complex (P4)
Synthesis of P4 is similar with P1, yield red solid (0.303 g,
62.4%). FTIR (KBr; cmꢁ1): 3033, 2922, 2858, 1555 (C@N), 1508
(C@C), 1035 (CAOAM), 502 (MAN). Anal. calcd. for [C99H104CdCl2-
1,10-Phenanthroline-5,6-dione [18] (0.66 g, 3.15 mmol) and
6-bromo-9-octyl-3-formyl carbazole (0.837 g, 3 mmol) were dis-
solved in 100 ml of glacial acetic acid, and the resulting solution
was refluxed for 3 h in the presence of 9.68 g of ammonium
acetate. After cooling to room temperature, the resulting solution
neutralized to pH 6.4 with ammonium and then the yellow precip-
itation was gained, collected and dried in vacuum at 60 °C, an or-
ange yellow powder was yield (1.29 g, 75%). 1H NMR(DMSO, d,
ppm): 0.84 (t, 3H), 1.05-1.38 (m, 10H), 1.85 (m, 2H), 4.75 (t, 2H),
7.31 (d, 1H), 7.58 (d, 1H), 7.73 (d, 3H), 8.08 (d, 1H), 8.35 (s, 1H),
8.78 (s, 1H), 8.93–9.00 (m, 2H), 9.02 (s, 2H),13.7 (s, 1H). FI-IR
(KBr, cmꢁ1): 3030 (HAC@C), 2921, 2875, 1618 (C@N),
1552(C@C). Anal. Calcd for [C33H30BrN5]: C, 68.75; H, 5.24; Br,
13.86; N, 12.15; Found: C, 70.03; H, 5.29; Br, 13.91; N, 12.22.
N10]: C, 73.52; H, 6.48; N, 8.66; Cl, 4.38; found: C, 73.12; H, 6.45; N,
ꢁ
8.61. Mn ¼ 14:5 kg=mol, PDI = 1.38.
3. Results and discussion
3.1. Characterization of ligand, complexes and polymeric metal
complexes
Fig. 1 shows 1H NMR of the ligand BPIK. 9.02 ppm, 8.93–
9.00 ppm were attributed to protons characteristic absorption peak
of phenanthroline. There are haracteristic signals at 7.31 ppm,
7.58 ppm, 8.08 ppm, 8.35 ppm, 8.78 ppm corresponded to the pro-
tons of carbazole. The signals for protons in the long alkyl chain are
located at 0.84 ppm, 1.05–1.38 ppm, 1.85 ppm. Signal at around
13.7 ppm is assigned to the proton of the NAH group. Appearance
of protons characteristic absorption peak of NAH and the disap-
pearance of protons characteristic absorption peak of HAC@O at
10.14 ppm proved fully that the ligand BPIK have been synthesized
successfully.
2.4.5. Synthesis of metal complex Zn(BPIK)2 (6)
Synthesis of Zn(BPIK)2 is similar with Cd(BPIK)2, yield bright
yellow solid (0.763 g, 57%). FTIR (KBr; cmꢁ1): 3010, 2911, 2843,
1581 (C@N), 1528 (C@C), 1095 (CAOAM), 513 (MAN). Anal. calcd.
for [C70H68Br2N10O4Zn]: C, 62.81; H, 5.12; Br, 11.94; N, 10.46; O,
4.78; Zn, 4.89; found: C, 63.05; H, 5.15; N, 10.58.
Fig. 2a shows the IR spectra of the ligand BPIK. According to
Fig. 2a, absorption signals of CAH stretching vibration were found
in 3035 cmꢁ1, 2921 cmꢁ1, and 2875 cmꢁ1. The sharp absorption
peaks at 1618 cmꢁ1 and 1552 cmꢁ1 are assigned to stretching fre-
quency of C@N and C@C, respectively. Disappearance of the signal
stretching vibration peak at 1685 cmꢁ1 shows formyl group is not
existed which can also prove that the ligand BPIK was synthesized
successfully. Fig. 2a and Fig. 2b provide the IR spectra of metal
complexes of Zn(BPIK)2, Cd(BPIK)2 and polymeric metal complexes
P1–P4. The CAN stretching vibration peak of metal complexes Zn
2.4.6. Synthesis of metal complex Cd(BPIK)2 (7)
Cadmium chloride (0.497 g, 1 mmol) dissolved in 15 ml of
methanol and BPIK (1.15 g, 2 mmol) dissolved in DMF were added
in flack. NaOH (1 mol/L) was added dropwise under stirring until
the solution shows weak acid. The mixed solution was refluxed
for 6 h. After cooling to room temperature, the crude product
was gained by filtration, washed many times by ethanol and dried
under vacuum. The orange solid (0.681 g, 51%) was yielded. FTIR
(KBr, cmꢁ1): 3022, 2915, 2855, 1578 (C@N), 1535 (C@C), 1082
(CAOAM), 508 (MAN). Anal. calcd. for [C66H60Br2CdCl2N10]: C,
59.32; H, 4.53; Br, 11.96; Cd, 8.41; Cl, 5.31; N, 10.48; found: C,
59.75; H, 4.55; N, 10.56.
(BPIK)2 and Cd (BPIK)2 appeared at 1095 cmꢁ1 and 1082 cmꢁ1
,
while their N-metal stretching vibration peak appeared at
513 cmꢁ1, 508 cmꢁ1 respectively. However, CAN stretching vibra-
tion peak for polymer P1–P4 appears at 1041 cmꢁ1, 1068 cmꢁ1
,
1035 cmꢁ1, 1052 cmꢁ1, respectively and the corresponding N-me-
2.4.7. Synthesis of polymeric metal complex [17] (P1)
tal stretching vibration signal also appeared at 504 cmꢁ1
,
Zn(BPIK)2 (0.401 g, 0.3 mmol), Pd(OAc)2 (0.0029 g, 0.013 mmol),
tri-o-tolylphosphie (0.0220 g, 0.072 mmol), DMF (8 mL), triethyl-
amine (3 mL) and 1,4-divinyl-2-methoxyl-5-octyloxybenzene
[17] were added into the flask. The mixed solution was heated
slowly to 90 °C in the presence of nitrogen and reacted for 36 h.
After cooling to room temperature, the mixture was filtrated and
filtrate was poured in methanol. The precipitate was gained, dis-
solved in DMF and further purified with methanol. At last, the yel-
low solid (0.238 g, 51%) was yielded. FTIR (KBr; cmꢁ1): 3012, 2932,
2875, 1557 (C@N), 1503 (C@C), 1068 (CAOAM), 496 (MAN). Anal.
calcd for [C96H106N10O6Zn]: C, 76.48; H, 6.85; ꢁN, 8.66; O, 3.95;
found: C, 76.01; H, 6.95; N, 8.62;O, 3.92. Mn ¼ 13:1 kg=mol,
PDI = 1.31.
496 cmꢁ1, 502 cmꢁ1, 407 cmꢁ1. It is very clear that stretching
vibration of CAN and metal-N appear red-shift due to increase of
the
p
conjugation system after polymerization.
2.4.8. Synthesis of polymeric metal complex (P2)
Synthesis of P2 is similar with P1, yield red solid (0.283 g,
60.5%). FTIR (KBr; cmꢁ1): 3033, 2922, 2858, 1555 (C@N), 1508
(C@C), 1035 (CAOAM), 502 (MAN). Anal. calcd. for [C92H100CdCl2-
N10O2]: C, 70.78; H, 6.46; N, 8.97; O, 2.05; Cl, 4.54; found: C, 71.02;
ꢁ
H, 6.49; N, 9.01. Mn ¼ 13:8 kg=mol, PDI = 1.26.
2.4.9. Synthesis of polymeric metal complex (P3)
Synthesis of P3 is similar with P1, yield golden yellow solid
(0.267 g, 55%). FTIR (KBr; cmꢁ1): 3008, 2928, 2866, 1565 (C@N),
1511 (C@C), 1041 (CAOAM), 504 (MAN). Anal. calcd. for [C103H110-
N10O4Zn]: C, 76.48; H, 6.85; N, 8.66; O, 3.95; found: C, 76.01; H,
6.95; N, 8.62;O, 3.92. Mn ¼ 14:4 kg=mol, PDI = 1.42.
ꢁ
Fig. 1. 1H NMR spectra of BPIK in CDCl3 solution.