C. Liu et al. / Dyes and Pigments 101 (2014) 85e92
87
J ¼ 7.2 Hz, 2H, Ph), 6.81 (d, J ¼ 7.0 Hz, 1H, Ph), 6.75 (dd, J ¼ 8.4 Hz,
26.58, 24.87 (CH3). HRMS (EI): calcd. for C29H26N2O2Pt [M]þ
629.1642; found: 629.1620.
1H, Ph), 5.39 (s, 1H, CH), 2.91 (s, 3H, CH3), 1.88 (s, 3H, CH3), 1.62 (s,
3H, CH3). 13C NMR (100 MHz, CDCl3):
d
¼ 185.36, 183.51 (CO),
LSTP-4. Eluent: CH2Cl2/hexane (3:1, v/v). A yellow solid; Yield:
168.82, 163.19, 147.56, 147.41, 139.28, 137.42, 137.28, 129.08, 125.53,
123.77, 123.13, 122.04, 121.90, 117.56, 114.67 (Ar), 101.33 (CH), 28.01,
41.6%. 1H NMR (400 MHz, CDCl3):
d
¼ 8.68 (s, 1H, Py), 7.55 (d,
J ¼ 7.8 Hz, 1H, Ph), 7.37 (d, J ¼ 8.3 Hz, 1H, Py), 7.26e7.35 (m, 6H, Ph),
7.17e7.20 (m, 4H, Py and Ph), 7.01e7.03 (t, J ¼ 7.2 Hz, 2H, Ph), 6.75
(dd, J ¼ 8.4 Hz, 1H, Ph), 5.38 (s, 1H, CH), 2.36 (s, 3H, CH3), 1.97 (s, 3H,
CH3), 1.71 (s, 3H, CH3). 13C NMR (100 MHz, CDCl3):
d
¼ 185.60,
184.04 (CO), 165.15, 147.86, 147.64, 146.85, 139.07, 138.76, 138.49,
129.98, 129.07, 125.26, 123.42, 123.38, 122.97, 117.82, 117.28 (Ar),
102.29 (CH), 28.31, 26.83, 18.20 (CH3). HRMS (EI): calcd. for
C
29H26N2O2Pt [M]þ 629.1642; found: 629.1592.
LSTP-5. Eluent: CH2Cl2/hexane (3:1, v/v). A yellow solid; Yield:
40.6%. 1H NMR (400 MHz, CDCl3):
Ph), 7.44 (m, 1H, Ph), 7.26e7.28 (m, 2H, Py), 7.20e7.25 (m, 8H, Ph),
7.03e7.17 (t, J ¼ 7.2 Hz, 2H, Ph), 6.76 (d, J ¼ 8.4 Hz, 1H, Ph), 5.39 (s,
1H, CH), 1.97 (s, 3H, CH3), 1.72 (s, 3H, CH3). 13C NMR (100 MHz,
d
¼ 8.82 (s, 1H, Py), 7.54 (m, 1H,
CDCl3):
d
¼ 185.90, 184.13 (CO), 164.79, 157.53, 155.06, 148.36,
147.45, 138.96, 136.93, 135.70, 135.38, 129.12, 125.53, 125.46, 125.34,
123.84,123.23,123.03,118.12,118.06,117.55 (Ar),102.42 (CH), 28.23,
26.75 (CH3). HRMS (EI): calcd. for C28H23N2O2PtF [M ꢀ H]ꢀ
632.1313; found: 632.1341.
LSTP-6. Eluent: CH2Cl2/hexane (3:1, v/v). A yellow solid; Yield:
50.3%. 1H NMR (400 MHz, CDCl3):
d
¼ 9.14 (s, 1H, Py), 7.86 (dd,
J ¼ 8.6 Hz, 1H, Ph), 7.50 (d, J ¼ 8.6 Hz, 1H, Ph), 7.25e7.31 (m, 5H, Py
and Ph), 7.17e7.25 (m, 5H, Ph), 7.06e7.10 (m, 3H, Ph), 6.75 (dd,
J ¼ 8.5 Hz,1H, Ph), 5.40 (s,1H, CH),1.98 (s, 3H, CH3),1.71 (s, 3H, CH3).
13C NMR (100 MHz, CDCl3):
d
¼ 186.09, 184.10 (CO), 170.95, 149.82,
147.00, 144.39, 141.88, 135.37, 134.56, 129.24, 126.10 (Ar), 125.39
(CF3), 123.90, 121.65, 117.10, 116.49, 103.82 (Ar), 102.40 (CH), 28.24,
26.71 (CH3). HRMS (EI): calcd. for C29H23N2O2PtF3 [M]ꢀ 683.1359;
found: 683.1378.
LSTP-7. Eluent: CH2Cl2/hexane (2:1, v/v). A red solid; Yield:
36.7%. 1H NMR (400 MHz, CDCl3):
J ¼ 8.4 Hz, 1H, Ph), 7.32 (d, J ¼ 8.9 Hz, 1H, Py), 7.29 (s, 1H, Ph), 7.20e
7.25 (m, 7H, Py and Ph), 7.11e7.20 (m, 4H, Ph), 6.74 (d, J ¼ 14.8 Hz,
1H, Ph), 5.40 (s, 1H, CH), 2.00 (s, 3H, CH3), 1.71 (s, 3H, CH3). 13C NMR
d
¼ 9.13 (s, 1H, Py), 7.85 (d,
(100 MHz, CDCl3):
d
¼ 186.27, 184.16 (CO), 171.08, 150.52, 150.32,
146.66, 143.05, 139.81, 134.51, 129.31, 126.40, 124.32, 120.93, 117.09,
116.13, 116.09, 111.35 (Ar), 103.71 (CN), 102.51 (CH), 28.26, 26.67
(CH3). HRMS (EI): calcd. for C29H23N3O2Pt [M]þ 640.1438; found:
640.1451.
2.3. Luminescent oxygen sensing
A home-assembled flow cell and optical fiber were used for the
oxygen sensing. Typical oxygen film preparation is as follows.
IMPES-C polymer (Scheme 2) (10.0 mg) prepared according to the
literature [7] was dissolved in acetone (0.5 mL) and then the Pt
complex in CH2Cl2 (0.2 mL, 1.0 ꢂ 10ꢀ3 mol dmꢀ3) was added to the
solution. After thoroughly mixing, about 0.3 mL of the solution was
coated on a silica glass disk (diameter 1.6 cm). The solvent was
evaporated at room temperature and a transparent film was ob-
tained. The thickness of the film containing LSTP-1 was estimated
to be 15.8 mm from the weight of the film (6.1 mg) and the density
of the polymer (1.21 g cmꢀ3). The film thicknesses of the complexes
LSTP-2eLSTP-7 were estimated by the same method to be 16.0,17.3,
15.9, 16.3, 15.8, and 18.0 mm, respectively.
3. Results and discussion
3.1. Crystal structures
To further establish their molecular structures, a majority of
these Pt(II) complexes were subjected to X-ray single-crystal
Fig. 1. Perspective view of the crystal structure of Pt(II) complexes (30% probability
ellipsoids, hydrogen atom labels have been omitted for clarity).