E. Teknikel and C. Unaleroglu
JournalofPhotochemistry&PhotobiologyA:Chemistry385(2019)112073
5H), 7.40–7.37 (m, 2H) 7.32 (t, J = 7.8 Hz, 1H), 7.06–7.05 (d,
J = 4.3 Hz, 1H), 6.94–6.91 (m, 3H), 6.67 (d, J = 2.2 Hz, 1H). 13C NMR
(100 MHz, d-DMSO) δ 159.5, 157.2, 145.3, 142.9, 136.3, 133.3, 133.2,
133.0, 132.7, 130.8, 130.5, 129.8, 129.4, 128.6, 121.6, 120.2, 118.9,
117.22, 115.98. 19F NMR (376 MHz, d-DMSO) δ −136.2 (dd, J = 61.4,
HRMS (APCI): m/z calcd. for C40H25B2Br2F4N5O [M−H]−: 844.0548;
found: 844.0583.
Declaration of Competing Interest
The authors declare no conflict of interest.
Acknowledgement
30.3 Hz). HRMS (APCI): m/z calcd. for
358.1209; found: 358.1221.
C
21H9BF2N2O [M−H]−:
4.3. Synthesis of compound 5
This work was partially supported by Hacettepe University BAP
(FDK-2018-17171).
A mixture of BODIPY 2 (40.3 mg, 0.07 mmol) and pyrrole (0.5 mL)
were stirred at 40 °C until the UV analysis showed the total consump-
tion of 2. Crude product was purified on column chromatography using
ethyl acetate/hexane (1:10) as eluent. Yield: 90%. Black iridescent
solid, blue in solution. 1H NMR (400 MHz, d-DMSO) δ 11.03 (s, 1H),
7.74–7.52 (m, 5H), 7.45 (s, 2H), 7.28 (s, 1H), 6.84 (s, 1H), 6.44 (s, 1H).
13C NMR (100 MHz, d-DMSO) δ 149.50, 138.77, 136.12, 135.59,
133.65, 132.54, 131.28, 131.05, 129.25, 128.78, 126.98, 125.71,
120.73, 120.60, 111.90, 111.20, 108.65. 19F NMR (376 MHz, d-DMSO)
δ −139.43 (dd, J = 63.7, 31.8 Hz). HRMS (APCI): m/z calcd. for
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
References
C
19H11BBr3F2N3 [M−H]−: 564.8528; found: 564.8492.
4.4. General procedure for the synthesis of the dyads
To BromoBODIPY (4 or 5) (0.2 mmol) in acetonitrile (25 mL) was
added K2CO3 and phenol-BODIPY (2 or 3) (0.1 mmol in 10 mL acet-
onitrile). The reaction mixture was stirred at room temperature until
TLC analysis showed the complete consumption of phenol-BODIPY.
Then the mixture was filtrated to remove excess K2CO3. After removing
the solvent under vacuum, the product was isolated by column chro-
matography on silica gel using ethyl acetate/hexane (1:10) as eluent.
Dyad 1; Black iridescent solid, red in solution. Yield: 46%. 1H NMR
(400 MHz, CDCl3) δ 7.96 (d, J = 8.5 Hz, 2H), 7.79 (s, 1H), 7.59–7.41
(m, 10H), 7.19 (d, 2H, J = 8.3), 6.97 (s, 1H), 6.91 (d, J = 4.2 Hz, 1H),
6.80 (d, J = 3.3 Hz, 1H), 6.75 (s, 1H), 6.63 (d, J = 4.2 Hz, 1H), 6.46 (s,
1H). 13C NMR (100 MHz, CDCl3) δ 159.9, 158.9, 156.3, 145.6, 142.5,
142.3, 137.3, 134.5, 134.2, 134.1, 134.0, 132.8, 131.9, 131.4, 131.2,
130.5, 130.5, 130.3, 129.9, 129.4, 129.1, 128.9, 128.7, 128.4, 120.9,
118.3, 118.1, 109.8, 98.9. 19F NMR (376 MHz, CDCl3) δ −139.2 (dd,
J = 61.6, 30.0 Hz), −147.8 (dd, J = 54.4, 25.8 Hz). HRMS (APCI): (the
molecule fragmented through ether bridge during ionization) m/z
calcd. for C21H9BF2N2O [M−H]−: 358.1209; found: 358.1192. m/z
calcd. for C15H8BBr3F2N2O [M−H]−: 515.8242; found: 515.8211.
Dyad 2; Black iridescent solid, red in solution. Yield: 43%. 1H NMR
(400 MHz, CDCl3) δ 7.95 (d, J = 7.7 Hz, 1H), 7.89 (s, 1H), 7.70 (s, 1H),
7.64–7.49 (m, 11H), 7.31 (s, 1H), 7.06 (s, 1H), 6.97 (d, J = 4.0 Hz, 1H),
6.91 (d, J = 3.3 Hz, 1H), 6.82 (s, 1H), 6.69 (d,J = 4.0 Hz, 1H), 6.56 (s,
1H). 13C NMR (100 MHz, CDCl3) δ 160.5, 158.1, 154.7, 146.2, 143.3,
141.9, 137.1, 134.9, 134.9, 134.1, 133.9, 133.8, 132.5, 131.9, 131.1,
130.6, 130.5, 130.4, 130.3, 129.8, 129.5, 129.0, 128.8, 128.7, 128.4,
126.48, 120.8, 119.7, 119.6, 118.6, 109.4, 98.9. 19F NMR (376 MHz,
CDCl3)
δ -138.7 (dd, J = 61.1, 30.2 Hz), −147.7 (dd, J = 54.2,
26.0 Hz). HRMS (APCI): (the molecule fragmented through ether bridge
during ionization) m/z calcd. for C21H9BF2N2O [M−H]−: 358.1209;
found: 358.1161. m/z calcd. for C15H8BBr3F2N2O [M−H]−: 515.8242;
found: 515.8143.
Dyad 3; Black iridescent solid, purple in solution. Yield: 72%. 1H
NMR (400 MHz, CDCl3) δ 10.43 (s, 1H), 7.88–7.72 (m, 2H), 7.61 – 7.36
(m, 13H), 7.17 (d, J = 8.6 Hz, 1H), 7.09 (s, 1H), 6.94 (s, 1H), 6.88 (d,
J = 4.1 Hz, 1H), 6.81 (d, J = 3.5 Hz, 1H), 6.73 (s, 1H), 6.61 (d,
J = 4.0 Hz, 1H), 6.46 (s, 1H), 6.33 (s, 1H). 13C NMR (100 MHz, CDCl3)
δ 158.7, 155.9, 155.4, 154.54, 146.0, 143.1, 139.4, 138.8, 137.1,
135.8, 134.6, 134.0, 133.8, 133.0, 132.5, 130.5, 130.4, 130.2, 130.2,
129.7, 128.9, 128.6, 128.4, 127.1, 126.6, 125.6, 125.5, 125.5, 121.6,
120.9, 119.3, 118.9, 118.8, 118.4, 111.2. 19F NMR (376 MHz, CDCl3) δ
−138.9 (dd, J = 60.9, 29.9 Hz), −140.7 (dd, J = 65.9, 33.2 Hz).
4