SuPRAMoLECuLAR CHEMISTRy
3
that include alkylated (C16) and non-alkylated controls that
are self-assembled with both labile (ZnII) and non-labile
(FeII) metals. We also probe how the counterion type and
solvent system affect morphology of the non-labile system.
(MgSo4), filtered and concentrated in vacuo to give 2,
as a white solid: 2.58 g (89%), mp 57–58 °C (lit (31) mp
59.5 °C); 1H NMR (300 MHz, CDCl3): δ 7.07 (s, 2H, Ar-H), 3.95
(t, J = 7 Hz, 4H, oCH2), 1.80 (m, 4H), 1.46 (br m, 8H), 1.29 (br
m, 44H), 0.89 (br m, 6H); 13C NMR (125 MHz, CDCl3): δ 14.12,
22.69, 25.93, 29.05, 29.34, 29.37, 29.59, 29.61, 29.67, 29.69,
29.71, 31.93, 69.62, 114.66, 118.04, 149.04; MALDI-ToF MS
(m/z): Found: 739.4. Calcd (C38H68Br2o2 + Na)+: 739.3.
4',4''''-(4',5'-Bis(hexadecyloxy)[1,1':2',1''-terphenyl]-4,4''-di-
yl)-di[2,2':6',2''-terpyridine] (3): A mixture of toluene (150 mL),
water (150 mL) and EtoH (50 mL) in a round bottom flask
was deaerated with argon for 30 min. Then 2 (1.69 g,
2.36 mmol), 4-(2,2':6',2''-terpyridin-4'-yl)phenylboronic acid
(32) (2.50 g, 7.09 mmol), and Na2Co3 (3.75 g, 35.4 mmol)
were added. The stirred mixture was then evacuated in
vacuo and backfilled with argon (5X). Pd(PPh3)2Cl2 (334 mg,
472 μmol) was added and the mixture was refluxed for
48 h. After cooling to 25 °C, the organic layer was removed
in vacuo. The aqueous layer was extracted with CH2Cl2 (2X,
150 mLs each); the organic layers were combined, dried
(MgSo4) and filtered. The resultant pinkish solution was
concentrated in vacuo, dried, and the resultant solid was
recrystallised from EtoAc and hexane to give 3, as a white
Experimental
Chemicals were commercially purchased and used without
further purification. Thin layer chromatography was con-
ducted on flexible sheets (Baker-flex) precoated with Al2o3
(IB-F) or Sio2 (IB2-F) and visualised by uV light. Column
chromatography was conducted using basic Al2o3 (60-325
mesh, Brockman Activity I) or Sio2 (60-200 mesh, Fisher
Scientific). 1H NMR spectra were recorded on a Varian
500 MHz spectrometer. Electrospray ionisation (ESI) mass
spectra (MS) were obtained on a Synapt High Definition
Mass Spectrometry (HDMS) quadrupole/time-of-flight (Q/
ToF) mass spectrometer (Waters Corp., Milford, MA). For
the transmission electron microscopy (TEM) studies, solu-
tions were prepared with 0.1 μM in 5/1 MeCN/CHCl3 or 2/1
CHCl3/MeoH and cast onto carbon-coated copper grids
(300 mesh) using a JoEL JEM-1230 transmission electron
microscope. AFM height and phase images were obtained
on a Nanoscope III multimode microscope from Digital
Instruments operating in the tapping mode with alumin-
ium-coated AFM probe from (Nanosensors PPP-NCHR,
length 125 mm, width 30 mm, thickness 4 mm, 330 kHz
frequency).
1,2-Bis(hexadecyloxy)benzene (1): To a solution of cat-
echol (721 mg, 6.55 mmol) and 1-bromohexadecane
(5.00 g, 16.4 mmol) in MeCN (200 mL), K2Co3 (4.32 g,
26.2 mmol) was added, then the mixture was refluxed for
2 days. After cooling to 25 °C, the mixture was filtered, dried
in vacuo to give a solid that was dissolved in CHCl3 and
extracted (2X) with water, then washed with a brine solu-
tion. After drying (MgSo4), the organic solution was filtered
and concentrated in vacuo to give a white solid, which was
washed with hexane and dried to give 1, as a white solid:
3.08 g (84%), mp 51–52 °C (lit (30) mp 53–54 °C); 1H NMR
(500 MHz, CDCl3): δ 6.90 (s, 4H, ArH), 3.92 (t, J = 7 Hz, 4H,
oCH2), 1.82 (m, 4H), 1.48 (br m, 8H), 1.33 (br m, 44 H), 0.89
(t, J = 7 Hz, 6H); 13C NMR (125 MHz, CDCl3): δ 14.12, 22.69,
26.06, 29.36, 29.37, 29.45, 29.65, 29.66, 29.67, 29.71, 29.72,
31.93, 69.25, 114.14, 120.99, 149.25; MALDI-ToF MS (m/z):
Found: 559.5. Calcd (C38H70o2 + H)+; 559.5; Found: 581.5.
Calcd (C38H70o2 + Na)+: 581.5.
1
solid: 1.7 g (62%), mp 98 °C; H NMR (500 MHz, CDCl3): δ
8.75 (s, 4H, tpyH3',5'), 8.69 (d, J = 5 Hz, 4H, tpyH6,6''), 8.65 (d,
J = 8 Hz, 4H, tpyH3,3''), 7.86 (t, J = 8 Hz, 4H, tpyH4,4''), 7.82 (d,
J = 9 Hz, 4H, ArH), 7.32 (m, 8H, ArH, tpyH5,5''), 7.04 (s, 2H),
4.13 (t, J = 7 Hz, 4H, oCH2), 1.90 (m, 4H), 1.53 (m, 4H), 1.36
(m, 48H), 0.88 (t, J = 6 Hz, 6H); 13C NMR [125 MHz, CDCl3]: δ
13.86, 22.40, 25.83, 29.11, 29.21, 29.41, 29.43, 29.47, 29.48,
31.67, 69.32, 76.49, 76.75, 76.95, 77.00, 115.94, 118.50,
121.03, 123.43, 126.71, 130.22, 132.32, 135.96, 136.50,
142.07, 148.46, 148.82, 149.54, 155.60, 156.07; MALDI-
ToF MS (m/z): Found: 1173.8029. Calcd (C80H96N6o2 + H)+:
1173.7595.
(3)3Fe3 [
+6 ꢀꢁꢂ−6] (4) or [6Cl−] (4a):To a stirred solution of 3
(181.7 mg, 0.155 μmol) dissolved in CH2Cl2 (250 mL), MeoH
(50 mL) was gradually added. A solution of FeCl2(4H2o)
(3.23 mg, 0.163 μmol) in MeoH (20 mL) was added drop-
wise. The reaction mixture was stirred at 25 °C for 12 h.,
then concentrated and dried in vacuo to give a solid that
was chromatographed (Sio2) eluting with CH2Cl2:MeoH
(9:1) to give 4a, as a purple solid: 71 mg (35%). Conversion
to PF−6 counterion was achieved by dissolving this solid in
CHCl3/MeoH (4:1) and precipitating with NH4PF6 affording
1
the desired 4: mp > 300 °C; H NMR (500 MHz, CD3CN/
1,2-Dibromo-4,5-bis(hexadecyloxy)benzene
(2):
CDCl3 5:1): δ 9.16 (s, 12H, tpyH3',5'), 8.59 (d, J = 8 Hz, 12H,
tpyH3,3''), 8.23 (d, J = 8 Hz, 12H, ArH), 7.80 (t, J = 8 Hz, 12H,
tpyH4,4''), 7.64 (d, J = 8 Hz, 12H, ArH), 7.27 (s, 6H, ArH), 7.15
(d, J = 6 Hz, 12H, tpyH6,6''), 7.03 (dd, J1 = 8 Hz, J2 = 6 Hz,
12H, tpyH5,5''), 4.13 (t, J = 6 Hz, 12H, oCH2), 1.90 (m, 12H),
1.59 (m, 12H), 1.46 (m, 132H), 1.28 (m, 12H), 0.88 (m, 18H);
1,2-Bis(hexadecyloxy)benzene (2.00 g, 4.0 mmol) was dis-
solved in CH2Cl2 (150 mL) and cooled to 0 °C; then bromine
(1.43 g, 8.96 mmol) in CH2Cl2 (12 mL) was added dropwise
over ca. 2 h. The stirred mixture was warmed to 25 °C over
12 h, then quenched with sodium metabisulfate, dried