Paper
Journal of Materials Chemistry C
added to a round bottom flask containing 2 or 4 (2.1 equiv.), 0.11 mmol of 1,4-dibutoxy-2,5-diiodobenzene, 0.006 mmol of
diiodide core (1 equiv.), copper(I) iodide (0.05 equiv.), and Cl2Pd(PPh3)2, 0.006 mmol of CuI, and 10 mL of 1 : 1 THF : NEt3.
bis(triphenylphosphine)palladium(II) dichloride (0.05 equiv.) 1 : 1 CH2Cl2 : hexanes was used as the chromatography eluent,
under argon, and stirred overnight. The reaction was monitored and 3-DBPE-F5 was recrystallized from chloroform/methanol in
by TLC, and completion was judged based on the consumption 54% yield. 1H NMR (500 MHz, CDCl3): d 8.00 (d, 2H), 7.69 (d, 2H),
of the diiodide. Solvents were then removed in vacuo, and the 7.55 (t, 2H), 7.41 (t, 2H), 7.02 (s, 2H), 4.05 (t, 4H), 1.87 (quin, 4H),
resulting crude product was purified by flash column chromato- 1.57 (sext, 4H), 1.00 (t, 6H). 13C NMR (125 MHz, CDCl3): d 165.2,
graphy and recrystallization, details of which are described for 153.7, 145.7 (d, J = 252 Hz), 141.7 (d, J = 252 Hz), 137.5 (d, J =
each target compound below.
252 Hz), 134.4, 132.2, 130.7, 130.3, 127.9, 124.5, 116.9, 114.2,
4-BP-F5. 4-BP-F5 was prepared according to the general 109.4, 93.2, 91.5, 69.4, 53.8, 31.4, 19.2, 13.9.
Sonogashira procedure, using 1.53 mmol of 2, 0.70 mmol of
4-PE-F5. 4-PE-F5 was prepared according to the general
4,40-diiodobiphenyl, 0.035 mmol of Cl2Pd(PPh3)2, 0.035 mmol Sonogashira procedure, using 0.26 mmol of 2, 0.13 mmol of
of CuI, and 30 mL of 5 : 1 THF : NEt3. 1 : 1 CH2Cl2 : hexanes was compound 6, 0.007 mmol of Cl2Pd(PPh3)2, 0.007 mmol of CuI,
used as the chromatography eluent, and the product was and 12 mL of 5 : 1 THF : NEt3. 1 : 1 CH2Cl2 : hexanes was used as
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recrystallized from hexanes in 44% yield. H NMR (500 MHz, the chromatography eluent, and 4-PE-F5 was recrystallized
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CDCl3): d 8.04 (d, 2H), 7.68 (d, 2H), 7.62 (d, 2H), 7.58–7.53 (m, from acetone/water in 75% yield. H NMR (500 MHz, CDCl3):
6H), 7.44 (t, 2H), 5.50 (s, 4H). 13C NMR (125 MHz, CDCl3): d 8.02 (d, 2H), 7.67 (d, 2H), 7.58-7.41 (m, 12H), 5.50 (s, 4H).
d 165.5, 145.7 (d, J = 252 Hz), 141.5 (d, J = 252 Hz), 140.5, 137.5 13C NMR (125 MHz, CDCl3): d 165.3, 145.9 (d, J = 252 Hz), 141.8 (d,
(d, J = 252 Hz), 134.2, 132.3, 131.8, 131.0, 130.6, 128.1, 126.9, J = 252 Hz), 137.5 (d, J = 252 Hz), 134.2, 132.3, 131.5, 131.4, 130.9,
124.0, 122.3, 109.3, 94.3, 88.8, 53.9.
130.6, 128.2, 123.8, 123.3, 123.1, 109.3, 94.2, 91.0, 89.8, 54.0.
4-BT-F5. 4-BT-F5 was prepared according to the general
4-PE-H5. 4-PE-H5 was prepared according to the general
Sonogashira procedure, using 0.82 mmol of 2, 0.41 mmol of Sonogashira procedure, using 0.55 mmol of 4, 0.25 mmol of
4,40-diiodobithiophene, 0.02 mmol of Cl2Pd(PPh3)2, 0.02 mmol compound 6, 0.013 mmol of Cl2Pd(PPh3)2, 0.013 mmol of CuI,
of CuI, and 24 mL of 5 : 1 THF : NEt3. 1 : 1 CH2Cl2 : hexanes was and 12 mL of 5 : 1 THF : NEt3. 1 : 1 CH2Cl2 : hexanes was used as
used as the chromatography eluent. 4-BT-F5 was recrystallized the chromatography eluent, and 4-PE-H5 was recrystallized
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from acetone/water in 63% yield. H NMR (500 MHz, CDCl3): from acetone/water in 22% yield. H NMR (500 MHz, CDCl3):
d 8.03 (d, 2H), 7.65 (d, 2H), 7.54 (t, 2H), 7.43 (t, 2H), 7.17 (d, 2H), d 8.06 (d, 2H), 7.68 (d, 2H), 7.56–7.49 (m, 10H), 7.44–7.36
7.13 (d, 2H). 13C NMR (125 MHz, CDCl3): d 165.2, 145.8 (d, J = (m, 12H), 5.45 (s, 4H). 13C NMR (125 MHz, CDCl3): d 166.1,
252 Hz), 141.8 (d, J = 252 Hz), 137.5 (d, J = 252 Hz), 138.6, 134.0, 135.8, 134.2, 131.9, 131.7, 131.5, 130.8, 128.6, 128.4, 128.3, 128.2,
133.1, 132.3, 131.0, 130.3, 128.3, 124.1, 123.5, 122.4, 109.3, 93.2, 123.6, 123.3, 123.0, 94.1, 91.1, 90.3, 67.2.
87.7, 54.0.
3-PE-F5. 3-PE-F5 was prepared according to the general
4-DMF-F5. 4-DMF-F5 was prepared according to the general Sonogashira procedure, using 0.48 mmol of 2, 0.24 mmol of
Sonogashira procedure, using 0.26 mmol of 2, 0.13 mmol of 1,4-diiodobenzene, 0.012 mmol of Cl2Pd(PPh3)2, 0.012 mmol of
2,7-diiodo-9,9-dimethylfluorene, 0.007 mmol of Cl2Pd(PPh3)2, CuI, and 12 mL of 5 : 1 THF : NEt3. 1 : 1 CH2Cl2 : hexanes was used
0.007 mmol of CuI, and 12 mL of 5 : 1 THF : NEt3. 1 : 1 CH2Cl2 : as the chromatography eluent, and 3-PE-F5 was recrystallized
hexanes was used as the chromatography eluent, and 4-DMF- from acetone in 61% yield. 1H NMR (500 MHz, CDCl3): d 8.02 (d,
F5 was then recrystallized from acetone/water in 75% yield. 2H), 7.69 (d, 2H), 7.56 (t, 2H), 7.48 (s, 4H), 7.43 (t, 2H), 5.5 (s, 4H).
1H NMR (500 MHz, CDCl3): d 8.02 (d, 2H), 7.74–7.69 (m, 4H), 13C NMR (125 MHz, CDCl3): d 165.3, 145.8 (d, J = 252 Hz), 141.8
7.63 (s, 2H), 7.56 (t, 2H), 7.49–7.41 (m, 4H), 5.52 (s, 4H), 1.57 (d, J = 252 Hz), 137.5 (d, J = 252 Hz), 134.3, 132.3 131.4, 130.9,
(s, 6H). 13C NMR (125 MHz, CDCl3): d 165.4, 154.1, 145.7 (d, J = 130.6, 128.2, 123.8, 123.3, 109.4, 94.2, 89.8, 53.9.
252 Hz), 141.7 (d, J = 252 Hz), 139.0, 137.5 (d, J = 252 Hz), 134.2,
132.3, 130.84, 130.8, 130.5, 128.0, 125.8, 124.2, 122.0, 120.2, Sonogashira procedure, using 0.67 mmol of 4, 0.33 mmol of
109.4, 95.5, 88.3, 53.9, 47.0, 26.8. 1,4-diiodobenzene, 0.02 mmol of Cl2Pd(PPh3)2, 0.02 mmol of
3-PE-H5. 3-PE-H5 was prepared according to the general
4-TMBP-F5. 4-TMBP-F5 was prepared according to the CuI, and 12 mL of 5 : 1 THF : NEt3. 3 :1 CH2Cl2: hexanes was used
general Sonogashira procedure, using 0.11 mmol of compound as the chromatography eluent, and 3-PE-H5 was recrystallized
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9, 0.24 mmol of 2, 0.01 mmol of Cl2Pd(PPh3)2, 0.01 mmol of from acetone/water in 70% yield. H NMR (500 MHz, CDCl3): d
CuI, and 6 mL of 5 : 1 THF : NEt3. 1 : 1 CH2Cl2 : hexanes was used 8.02 (d, 2H), 7.65 (d, 2H), 7.53–7.28 (m, 18H). 13C NMR (75 MHz,
as the chromatography eluent, and 4-TMBP-F5 was recrystal- CDCl3): d 166.1, 135.8, 134.2, 131.9, 131.7, 131.6, 130.8, 128.6,
lized from acetone/water in 43% yield. 1H NMR (500 MHz, 128.4, 128.3, 128.2, 123.6, 123.2, 94.2, 90.2, 67.1.
CDCl3): d 7.99 (d, 2H), 7.65 (d, 2H), 7.51 (t, 2H), 7.38 (t, 2H), 7.27
(s, 4H), 5.49 (s, 4H), 1.91 (s, 12H). 13C NMR (125 MHz, CDCl3):
d 165.5, 145.8 (d, J = 252 Hz), 141.8 (d, J = 252 Hz), 140.3, 137.5
(d, J = 252 Hz), 135.8, 134.4, 132.2, 130.8, 130.63, 130.4, 127.8,
124.3, 121.6, 109.5, 95.1, 87.3, 54.0, 19.5.
Results and discussion
Molecular design and synthesis
3-DBPE-F5. 3-DBPE-F5 was prepared according to the general In contrast to our previous three-ring PEs that twist in response
Sonogashira procedure, using 0.23 mmol of compound 2, to ArF–ArH interactions of
a central terephthalate with
J. Mater. Chem. C
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