122.3–121.7 (br), 119.2–118.8 (br), 118.5–117.8 (br), 35.8–35.6
(br), 31.7 ppm. MALDI-TOF MS: m/z calcd for C258H240B6N36O6
4005.77; found 4005.44 [M]+. UV-vis (toluene): lmax = 567 nm (Q
band).
128.70, 128.66, 127.7, 126.41, 126.36, 124.9, 124.75, 121.7, 118.26,
118.20, 118.06, 117.9, 117.8, 117.6, 35.8, 31.7 ppm. 11B NMR
(96 MHz, CDCl3): d = -14.9 ppm (brs). MALDI-TOF MS: m/z
calcd for C114H100B2N12O2 1690.83; found 1690.02 [M]+. UV-vis
(toluene): lmax = 566 nm (Q band).
4.4. 1,2-Bis(4-hydroxyphenyl)-3,4,5,6-tetraphenylbenzene
4.6. 1-{4-[2,9(10),16(17)-Tris(tert-butyl)subphthalocya-
ninatoboron(III)]oxyphenyl}-2,3,4,5,6-pentaphenylbenzene,
mono-[B(SubPc)] 3
2,3,4,5-Tetraphenyl-2,4-cyclopentadien-1-one
(275
mg,
0.72 mmol) was refluxed with 1,2-bis(4-methoxyphenyl)acetylene
(170 mg, 0.71 mmol) in diphenylether (2 mL) for 12 h. The reaction
mixture was poured into ethanol. The collected precipitate was
washed with excess ethanol and n-hexane. Recrystallization
from toluene afforded 1,2-bis(4-methoxyphenyl)-3,4,5,6-
tetraphenylbenzene as a pale brown solid (195 mg, 0.33 mmol;
yield 46%). 1H NMR (300 MHz, CDCl3): d = 6.88–6.78 (m, 20H;
Ph), 6.71 (d, J = 8.8 Hz, 4H; Ph b to -OMe), 6.41 (d, J = 8.8 Hz,
4H; Ph a to -OMe), 3.61 ppm (s, 6H; Me). 13C NMR (75 MHz,
CDCl3): d = 156.9, 140.9, 140.8, 140.6, 140.2, 133.2, 132.4, 131.4,
129.09, 126.6, 126.5, 125.05, 112.2, 54.9 ppm. ESI-TOF MS: m/z:
calcd for C44H34O2: 594.26; found: 617.3 [M+Na]+.
To a solution of 1,2-bis(4-methoxyphenyl)-3,4,5,6-tetraphenyl-
benzene (122 mg, 0.20 mmol) in dichloromethane (5 mL) was
added dropwise boron tribromide (0.35 mmol) in dichloromethane
(0.85 mL) at -40 ◦C. The mixture was stirred for an additional 18
h as the temperature increased to 25 ◦C, followed by quenching by
addition of water (5 mL). The target material was extracted with
ethyl acetate and dried over anhydrous sodium sulfate. Colourless
powder (113 mg, 0.20 mmol; 97%). 1H NMR (300 MHz, CDCl3):
d = 7.00 (s, 2H; OH), 6.87–6.75 (m, 20 H; Ph), 6.63 (d, J = 8.5 Hz,
4H; Ph b to OH), 6.35 ppm (d, J = 8.5 Hz, 4H; Ph a to OH).
13C NMR (75 MHz, CDCl3): d = 154.3, 141.3, 141.1, 140.8, 140.2,
132.6, 131.7, 126.71, 126.66, 125.2, 125.13, 114.0 ppm. ESI-TOF
MS: m/z: calcd for C42H30O2: 566.22; found: 566.2 [M - H]-.
A mixture of 1-(4-hydroxyphenyl)-2,3,4,5,6-pentaphenylbenzene19
(75 mg, 0.14 mmol) and Cl[B(SubPc)] (26 mg, 0.043 mmol)
was refluxed in dry toluene/1,4-dioxane (4 mL/2 mL) for 34 h.
The residue was purified by silica-gel chromatography with n-
hexane/ethyl acetate (5/1, v/v) as the eluent, followed by a second
silica-gel column with the gradient solvent system of toluene/ethyl
acetate (100/0 to 55/1, v/v). The desired product was eluted
from a Sephadex column with ethyl acetate as a purple solid
1
(7.8 mg, 7 mmol; 16% based on Cl[B(SubPc)]). H NMR (300
MHz, CDCl3): d = 8.86, 8.83 (s, s, 3H; SubPc-a(1)), 8.76, 8.73 (d,
d, J = 8.4 Hz, 3H; SubPc-a(4)), 7.95 (d, 3H, J = 8.4 Hz, SubPc-b),
6.82–6.60 (m, 21H, Ph), 6.57 (d, 4H, J = 6.7 Hz, 2,6-Ph a to central
Ph), 6.12 (d, J = 8.5 Hz, 2H; Ph b to O-B(SubPc)), 4.91 (d, J =
8.5 Hz, 2H; Ph a to O-B(SubPc)), 1.57–1.55 ppm (m, 27H; tBu).
13C NMR (75 MHz, CDCl3): d = 153.7, 140.7, 140.33, 140.25,
139.9, 131.8, 131.4, 131.2, 127.8, 126.5, 125.0, 124.9, 121.6, 118.6,
117.5, 35.8, 31.7 ppm. 11B NMR (96 MHz, CDCl3): d = -15.0
ppm (brs). MALDI-TOF MS: m/z calcd for C78H65BN6O 1112.53;
found 1112.53 [M]+. UV-vis (toluene): lmax = 566 nm (Q band).
4.7. [2,9(10),16(17)-tris(tert-butyl)subphthalocya-
ninatoboron(III)oxy]benzene, PhO[B(SubPc)] 4
A mixture of Cl[B(SubPc)] (21 mg, 0.035 mmol) and phenol
(19 mg, 0.2 mmol) was refluxed in dry toluene (3 mL) in the
dark for 3.5 h. After removal of the solvent, the residue was re-
dissolved in chloroform (20 mL) and successively washed with
saturated aqueous sodium hydrogencarbonate (20 mL) and brine
(20 mL). The organic layer was dried over anhydrous sodium
sulfate. The titled material was eluted from a silica-gel column
chromatography with n-hexane/ethyl acetate (8/1, v/v) as the
eluent. PhO[B(SubPc)] 4 was obtained as purple solid (22 mg,
4.5. 1,2-Bis{4-[2,9(10),16(17)-tris(tert-butyl)subphthalocya-
ninatoboron(III)]oxyphenyl}-3,4,5,6-tetraphenylbenzene,
bis-[B(SubPc)] 2
A
mixture of 1,2-bis(4-hydroxyphenyl)-3,4,5,6-pentaphenyl-
benzene (29 mg, 0.050 mmol) and Cl[B(SubPc)] (85 mg,
0.14 mmol) was refluxed in dry toluene (4 mL) and ethyl acetate
(0.5 mL) for 88 h. After removal of the solvent under reduced
pressure, the residue was dissolved in chloroform (20 mL) and
successively washed with saturated aqueous sodium hydrogencar-
bonate (20 mL) and brine (20 mL). The organic layer was dried
over anhydrous sodium sulfate. The residue was purified by silica-
gel column chromatography with hexane/ethyl acetate (5/1, v/v)
as the eluent, followed by passing through a Sephadex column with
ethyl acetate as the eluent. Purple solid (47 mg, 0.028 mmol; 55%
based on 1,2-bis(4-hydroxyphenyl)-3,4,5,6-pentaphenylbenzene).
1H NMR (300 MHz, CDCl3): d = 8.83, 8.76 (s, s, 6H; SubPc-a(1)),
8.67, 8.60 (d, d, J = 8.4 Hz, 6H; SubPc-a(4)), 7.94–7.89 (brm, 6H;
SubPc-b), 6.79–6.56 (m, 16H; Ph), 6.48 (d, J = 7.2 Hz, 4H; 3,6-Ph
a to central Ph), 5.91 (d, 4H, J = 8.4 Hz, Ph b to O-B(SubPc)),
5.02–4.72 (m, 4H; Ph a to O-B(SubPc)), 1.54, 1.52, 1.51 (s, s, s,
54H; tBu). 13C NMR (126 MHz, CDCl3): d = 153.60, 153.59,
153.55, 153.53, 151.30, 151.24, 151.10, 151.01, 150.97, 150.84,
149.86, 149.82, 140.9, 140.5, 140.1, 139.95, 139.91, 133.6, 131.75,
131.69, 131.5, 131.33, 131.25, 131.19, 131.13, 128.75, 128.71,
1
0.033 mmol; 95% based on Cl[B(SubPc)]). H NMR (300 MHz,
CDCl3): d = 8.88, 8.85 (s, s, 3H; SubPc-a(1)), 8.77, 8.75 (d, d, J =
8.4 Hz, 3H; SubPc-a(4)), 7.97 (d, J = 8.4 Hz, 3H; SubPc-b), 6.75
(dd, J = 8.4, 7.4 Hz, 2H; Ph b to O-B(SubPc)), 6.60 (t, J = 8.4 Hz,
1H; p-Ph), 5.39 (d, J = 7.4 Hz, 2H; Ph a to O-B(SubPc)), 1.55,
1.54 ppm (s, s, 27H; tBu). 11B NMR (96 MHz, CDCl3): d = -14.8
ppm (brs). MALDI-TOF MS: m/z: calcd for C42H41BN6O: 656.34;
found: 656.36 [M]+. UV-vis (toluene): lmax = 567 nm (Q band).
4.8 Analytical methods of steady-state fluorescence/excitation
anisotropy measurement
Fast energy migration redistributes the polarization at the excited
state, where it is expected to be reduced the ratio of fluorescence
anisotropy (r). Then, steady-state fluorescence anisotropy was
observed in polyethylene glycol (PEG; Mw = ca. 200) as viscous
medium to minimize molecular reorientation.3 A comparison is
available to evaluate the qualitative energy migration.
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 10047–10054 | 10053
©