Supramolecular Chemistry
9
solution was stirred continuously for 30 min followed by
the addition of 3 ml Et3N and 3 ml BF3.OEt2, and stirred
for 3 h. The reaction mixture was washed three times with
water and dried over MgSO4. After filtration, the solvent
was evaporated, and the residue was purified by silica gel
column chromatography (dichloromethane/ethylacetate,
10:1), orange solid (184 mg, 50% yield). 1H NMR
[400 MHz, CDCl3]: 7.85 (bs, 2H, PyH), 7.52 (d, 2H,
ArH), 7.19 (d, 2H, ArH), 6.99 (d, 2H, PyH), 6.49 (d, 2H,
PyH), 4.09 (t, 2H, CH) 3.51 (t, 2H, CH), 2.06 (m, 2H, CH).
11B NMR [128.3 MHz, CDCl3]: 20.4891 (s, 1B); 19F
NMR [376.83 MHz, CDCl3]: 2144.76 (dd, 2F) 2144.91
(dd, 1F); 13C NMR [100 MHz, CDCl3]: 161.39, 147.30,
143.78, 134.72, 132.20, 131.73, 126.67, 118.12, 115.09
64.79, 47.68, 29.06. Anal. calcd for (%) C18H16BF2N5O:
C, 58.88; H, 4.39; N, 19.07; found: C, 59.23; H, 4.33; N,
19.17.
CH), 2.44 (m, 6H, CH). lmax: 495 nm. 11B NMR
[128.3 MHz, CDCl3]: 20.4891 (s, 3B); 19F NMR
[376.83 MHz, CDCl3]: 2144.75 (dd, 1F), 2144. 60 (dd,
1F), 2144.67 (dd, 2F), 2144.49 (dd, 2F); 13C NMR
[100 MHz, CDCl3]: 166.23, 161.80, 160.15, 159.62,
159.51, 148.15, 144.52, 143.78, 133.46, 133.36, 132.41,
131.73, 127.74, 126.67, 115.50, 115.46, 110.16, 110.08,
108.58, 65.42, 63.10, 48.31, 30.78. Anal. calcd for (%)
C70H60B3F6N15O7: C, 61.38; H, 4.42; N, 15.34; found: C,
61.44; H, 4.54; N, 15.76.
4.10 Synthesis of Bodipy-Zn (II) complexes
The Zn (II) complexes of Bodipys were prepared
according to the known procedures (14, 28) and used by
purification techniques. To the solution of metal ion
(1.0 mmol) in 20 ml hot methanol, a solution of equivalent
Bodipy ligands in 20 ml hot methanol was added drop
wise. The reaction mixture was refluxed at 508C for 24 h.
The resulting substances were filtered and washed with hot
methanol and water.
4.8 Synthesis of BODIPY-NPB
To a mixture of CHCl3:MeOH:H2O (ratio 10:1:1), 1
(NPB) (177 mg, 1 mmol) and 1.1 equiv. of 6 (403 mg,
1.1 mmol) were added. Then, 0.3 equiv of sodium
ascorbate was added to this mixture and stirred for
5 min, followed by the addition of 0.15 equiv. of CuSO4.
The heterogeneous mixture was stirred vigorously for 96 h.
(until TLC analysis indicated to the consumption of the
starting material). After the reaction completed, the
solvents were evaporated, and the residue was extracted
with CHCl3–water. The combined organic phase was
concentrated and purified by column chromatography
(CHCl3, as an eluent) (397 mg, 73% yield). 1H NMR
[400 MHz, CDCl3]: 7.91 (bs, 2H, PyH), 7.84 (d, 1H, ArH),
7.78 (s, 1H, CH) 7.55 (t, 1H, ArH), 7.54 (d, 2H, ArH), 7.31
(d, 1H, ArH), 7.03 (t, 1H, ArH), 7.00 (d, 2H, PyH), 6.54
(dd, 2H, PyH), 5.38 (s, 1H, CH), 5.32 (s, 2H, CH) 4.67 (t,
2H, CH) 4.08 (t, 2H, CH), 2.49 (m, 2H, CH). lmax:
495 nm. 11B NMR [128.3 MHz, CDCl3]: 20.4891 (s, 1B);
19F NMR [376.83 MHz, CDCl3]: 2144.73 (dd, 2F)
2144.99 (dd, 1F); 13C NMR [100 MHz, CDCl3]: 160.79,
151.42, 147.15, 143.43, 140.11, 134.73, 134.28, 132.41,
131.35, 126.67, 125.62, 123.46, 121.12, 118.30, 115.29
114.46, 64.31, 53.40, 29.73. Anal. calcd for (%)
C27H23BF2N6O4: C, 59.58; H, 4.26; N, 15.44; found: C,
59.34; H, 4.22; N, 15.23.
Supporting Information Available
CCDC numbers 844776–844779 contain the supplemen-
tary crystallographic data (CIF) for this article. These data
can be obtained free of charge from the Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (Fax: þ44-
ccdc.cam.ac.uk). The additional DFT calculations and
figures are available in PDF formats.
Acknowledgements
This work was supported by the Scientific Research Projects
Foundation of Selcuk University (SUBAP-Grant Number
11101003).
References
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4.9 Synthesis of BODIPY-PBPB
The compound was prepared from 2 (PBPB) and 6
according to the procedure described for BODIPY-NPB
1
(480 mg, 35% yield). H NMR [400 MHz, CDCl3]: 7.83
(bs, 6H, PyH), 7.64 (s, 2H, ArH), 7.46 (d, 6H, ArH), 7.41
(s, 1H, ArH), 6.94 (d, 6H, ArH), 6.87 (d, 6H, PyH), 6.46
(dd, 6H, PyH), 5.39 (s, 1H, CH), 5.21 (s, 2H, CH), 5.15 (s,
2H, CH), 4.82 (s, 4H, CH), 4.61 (t, 6H, CH), 4.02 (t, 6H,