Y. Shi et al. / Inorganica Chimica Acta 427 (2015) 259–265
261
bottom flask under a nitrogen atmosphere, then the mixture was
stirred at room temperature. The monitoring method for the reac-
tion and the purification process of the products is similar to the
synthesis of 5. The fine yellow powder 6 was obtained and weighed
DMF (30 mL) in a 100 mL round bottom flask under a nitrogen atmo-
sphere, then the mixture was stirred at room temperature. The mon-
itoring method for the reaction and the purification process of the
products is similar to the synthesis of 5. Yield = 64%. m.p. = 222–
5.68 g. Yield = 78%. m.p. = 220–222 °C. FT-IR
m
(cmꢀ1): 3085.05
225 °C. FT-IR m
(cmꢀ1): 3125.89 (C–H, aromatic), 1596.91, 1494.32,
(C–H, aromatic), 2216.79 (–C„C–), 1606.00, 1514.79, 1467.48
(–C@C–), 832.00 (P–F). 1H NMR (400 MHz, DMSO-d6): 7.74 (d,
J = 8.3 Hz, 1H), 7.58 (d, J = 3.3 Hz, 1H), 7.46 (s, 2H), 7.38 (d,
J = 8.2 Hz, 1H), 6.40 (s, 4H), 5.28 (s, 1H). 13C NMR (101 MHz,
DMSO-d6): 153.89(2C), 133.78(4C), 131.37(4C), 129.50(2C),
128.96(2C), 128.79(4C), 122.02(2C), 120.62(4C), 119.95(2C),
89.73(2C), 88.29 (2C), 78.13(5C), 75.87(4C). ESI-MS (m/z): calcd
for C39H27FeO+2 [M]+ 583.4875, found 583.4864 (cation+). Anal. Calc.
for C39H27F6FeO2P (728.4 g molꢀ1): C, 64.30; H, 3.74; O, 4.39.
Found: C, 62.05; H, 3.46; O, 4.13%.
1456.69 (–C„C–), 825.83 (P–F). 1H NMR (400 MHz, Acetone-d6):
7.94 (d, J = 8.5 Hz,2H), 7.81 (d, J = 8.2 Hz, 2H), 7.70 (d, J = 8.2 Hz, 2H),
7.63–7.57 (m, 1H), 7.51 (d, J = 8.5 Hz, 2H), 7.47–7.45 (m, 3H), 6.53
(t, J = 6.3 Hz, 2H), 6.48 (d, J = 6.5 Hz, 2H), 6.35 (t, J = 5.8 Hz, 1H), 5.32
(s, 2H). 13C NMR (101 MHz, Acetone-d6): 152.82(1C), 139.04(1C),
137.11(1C), 132.54(1C), 132.07(2C), 131.38(2C), 128.94(2C), 128.78
(2C), 126.92(1C), 126.62(2C), 122.21(1C), 121.53(1C), 121.38(2C),
90.27(1C), 89.11(1C), 86.72(2C), 84.86(2C), 76.96(5C), 76.86(1C).
ESI-MS (m/z): calcd for C31H23FeO+ [M]+ 467.3685, found 467.3671
(cation+). Anal. Calc. for C31H23F6FeOP (612.3 g molꢀ1): C, 60.81; H,
3.79; O, 2.61. Found: C, 60.56; H, 3.51; O, 2.32%.
2.2.5. (
iron hexafluorophosphate (7)
g g
6-(4-Phenylethynyl)phenyl benzene) ( 5-cyclopentadienyl)
2.2.8. (
cyclopentadienyl) iron hexafluorophosphate (10)
g -
6-1,4-Bis((4-phenylethynyl)biphenoxyl)benzene) (g5
A 100 mL of round-bottom flask was charged with 3 (0.69 g,
3.1 mmol), Fc-Cl (1.00 g, 2.6 mmol), K2CO3 (1.44 g, 10.0 mmol),
Pd(PPh3)4 (0.005 g, 0.004 mmol), THF (50 mL), and water (10 mL).
The mixture was heated to reflux and stirred for 8 h. Then the mix-
ture was poured into a saturated water solution of KPF6 (200 mL),
and then the precipitate was filtered under reduced pressure as a
brown solid. The obtained residue was purified by column chroma-
tography on aluminum oxide (acetone as eluting agent) to give the
corresponding pure cross-coupling product 7 as a yellow powder
A 100 mL of round-bottom flask was charged with Cl-Fc-Cl (4.1 g,
10.0 mmol), 4 (5.5 g, 20.2 mmol), K2CO3 (2.7 g, 20.0 mmol), and DMF
(30 mL) in a 100 mL round bottom flask under a nitrogen atmo-
sphere, then the mixture was stirred at room temperature. The mon-
itoring method for the reaction and the purification process of the
products are similar to the synthesis of 6. Yield = 78%. m.p. = 223–
224 °C. FT-IR m
(cmꢀ1): 3113.52 (C–H, aromatic), 2215.56 (–C„C–),
1603.46, 1509.12, 1457.98 (–C@C–), 829.11 (P–F). 1H NMR
(400 MHz, DMSO-d6): 7.92 (d, J = 8.5 Hz, 4H), 7.81 (d, J = 8.1 Hz,
4H), 7.69 (d, J = 8.0 Hz, 4H), 7.59 (d, J = 3.2 Hz, 4H), 7.46–7.46 (m,
10H), 6.39 (s, 4H), 5.29 (s, 5H). 13C NMR (101 MHz, DMSO-d6):
153.44(2C), 139.00(2C), 136.94(2C), 132.06(4C), 131.37(4C), 129.98
(2C), 128.92(2C), 128.79(4C), 126.92(4C), 122.19(2C), 121.52(2C),
120.96(4C), 90.26(2C), 89.09(2C), 77.98(5C), 75.32(4C). ESI-MS (m/
z): calcd for C51H35FeO+2 [M]+ 735.6835, found 735.6820 (cation+).
Anal. Calc. for C51H35F6FeO2P (880.6 g molꢀ1): C, 69.56; H, 4.01; O,
3.63. Found: C, 69.31; H, 3.73; O, 3.34%.
(0.85 g, 1.6 mmol, 63%). m.p. = 223–225 °C. FT-IR
m
(cmꢀ1):
3104.87 (C–H, aromatic), 2218.83 (–C„C–), 1608.05, 1508.28,
1459.38 (–C„C–), 823.7 (P–F). 1H NMR (400 MHz, Acetone-d6):
8.10 (d, J = 8.2 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.62–7.59 (m, 0H),
7.47–7.46 (m, 1H), 7.02 (d, J = 6.5 Hz, 2H), 6.73 (t, J = 6.3 Hz, 2H),
6.63 (t, J = 6.1 Hz, 1H), 5.22 (s, 5H). 13C NMR (101 MHz, Acetone-
d6): 135.28(1C), 132.09(2C), 131.48(2C), 129.14(1C), 128.83(2C),
128.20(2C), 123.88(1C), 121.92(1C), 101.65(1C), 91.30(1C),
88.64(1C), 88.08(2C), 87.32(1C), 86.08(2C), 77.55(5C). ESI-MS (m/
z): calcd for C25H19Fe+ [M]+ 375.2715, found 375.2698 (cation+).
Anal. Calc. for C25H19F6FeP (520.2 g molꢀ1): C, 57.72; H, 3.68.
Found: C, 57.50; H, 3.43%.
2.3. Z-scan measurement
Open-aperture Z-scan measurements were carried out to deter-
mine the nonlinear transmission of laser light through the samples.
The Z-scan provides information about the nonlinear absorption
coefficient. The samples were prepared as transparent solutions
of 5.0 ꢁ 10ꢀ4 M in spectroscopic-grade acetonitrile. The samples
were placed in 1 mm cuvettes and then irradiated by plane-
polarized 5 ns laser pulses at 532 nm from the second harmonic
output of a Q-switched Nd:YAG laser. The laser pulse energy was
2.2.6. (
cyclopentadienyl) iron hexafluorophosphate (8)
g -
6-1,4-Bis(4-phenylethynyl)phenyl benzene) (g5
A 100 mL of round-bottom flask was charged with 3 (1.34 g,
6.0 mmol), Cl-Fc-Cl (1.00 g, 2.4 mmol), K2CO3 (1.73 g, 12.0 mmol),
Pd(PPh3)4 (0.005 g, 0.004 mmol), THF (50 mL), and water (10 mL).
The mixture was heated to reflux and stirred for 8 h. Then the mix-
ture was poured into a saturated water solution of KPF6 (200 mL),
and then the precipitate was filtered under reduced pressure as a
brown solid. The obtained residue was purified by column chroma-
tography on aluminum oxide (acetone as eluting agent) to give the
corresponding pure cross-coupling product 8 as a yellow powder
6 lJ, and the beam focal spot radius (x0) was 16 lm. The laser
was run in the single shot mode using a data acquisition program,
with an approximate interval of 3–4 s in between each pulse. This
low repetition rate prevents sample damage and cumulative
thermal effects in the medium.
Assuming a GAUSSIAN temporal profile, we expressed the normal-
ized energy transmittance T(z) as [34]:
(1.14 g, 1.63 mmol, 68%). m.p. = 226–228 °C. FT-IR
m
(cmꢀ1):
3118.75 (C–H, aromatic), 2216.66 (–C„C–), 1605.44, 1512.69,
1456.54 (–C„C–), 826.54(P-F). 1H NMR (400 MHz, DMSO-d6): 8.16
(d, J = 8.2 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.63–7.62 (m, 4H), 7.50–
7.47 (m, 6H), 7.13 (s, 4H), 4.99 (s, 5H). 13C NMR (101 MHz, DMSO-
d6): 134.71(1C), 132.12(2C), 131.49(2C), 129.17(1C), 128.85(2C),
128.32(2C), 124.02(1C), 121.91(1C), 100.99(1C), 91.41(1C),
88.66(1C), 85.93(2C), 78.88(2C). ESI-MS (m/z): calcd for C39H27Fe+
[M]+ 551.4895, found 551.4885 (cation+). Anal. Calc. for C39H27F6FeP
(696.4 g molꢀ1): C, 67.26; H, 3.91. Found: C, 67.01; H, 3.61%.
Z
þ1
h
i
1
2
TðzÞ ¼
ln 1 þ q0ðz0Þeꢀt dt
ð2Þ
pffiffiffi
p
q0ðz0Þ
ꢀ1
where q ðz0Þ ¼ bI0Leff ð1 þ z2=z2Þꢀ1, Leff ¼ ½1 ꢀ eꢀ ꢂ=
a
0; L is the sam-
a0L
0
0
ple thickness; z0 ¼ k
x
20=2 is the Rayleigh length; x0 is the beam
waist; k = 2p/k is the wave vector; k is the laser wavelength; z is
the sample position; I0 is the on-axis irradiance at the focus (z = 0).
The nonlinear absorption coefficient b can be determined by fit-
ting the Z-scan curves with Eq. (1). The nonlinear absorption
2.2.7. (
cyclopentadienyl) iron hexafluorophosphate (9)
g -
6-(4-Phenylethynyl)biphenoxy benzene) (g5
A 100 mL of round-bottom flask was charged with Fc-Cl (3.8 g,
10.0 mmol), 4 (5.5 g, 20.2 mmol), K2CO3 (2.7 g, 20.0 mmol), and
cross-section can be determined utilizing
r = hmb/N, where hm is
the excitation energy and N is the number of molecules per cm3.