Bang-Tun Zhao et al.
on Carlo-Erba 1106 instruments. X-Ray crystallographic (2 mL, excess) was added dropwise. The reaction
data for 5 were obtained using a Bruker SMART mixture was stirred at room temperature under N2 for
APEX II CCD diffractometer equipped with graphite 20 h. The organic phase was washed with water, dried
monochromated Mo Κα radiation (λ = 0.71073 Å) at over MgSO4, and evaporated to yield an oil residue,
293 K. The structure was solved by direct methods which was chromatographied on a silica column using
using SHELXS-97 and refined using SHELXL-97 methylene chloride/petroleum ether (10:1, V:V) to
1
by full-matrix least-squares methods on F2 [15,16]. give 3 as red-orange sticky oil in 89% yield. H NMR
Hydrogen atoms were located from expected geometry (CDCl3, ppm): δ: 7.80 (d, J = 8.0 Hz, 4 H, ArH), 7.35
and were isotropically refined by riding model. All (d, J = 8.0 Hz, 4 H, ArH), 4.16 (t, J = 4.6 Hz, 4 H,
non-hydrogen atoms were refined anisotropically TsOCH2), 3.68 (t, J = 4.4 Hz, 4 H, OCH2), 3.60
except those of the disordered fragments. The φ-ω (t, J = 6.6 Hz, 4 H, OCH2), 2.92 (t, J = 6.4 Hz, 4 H,
scan was used for absorption correction. Cyclic OSH2), 2.45(s, 6 H, ArCH3), 2.43(s, 6 H, SCH3).
voltammetry (CV) experiments were performed on
a CHI620C electrochemistry workstation in a three-
2.3.
Synthesis of calix[4]arene-tetrathiaful-
valene (5)
electrode system served as Pt working electrode
(2 mm, diameter), with Ag/AgCl and platinum wire acting
as reference and counter electrodes, respectively. The
UV absorption spectra were measured on a UV-3010
UV–vis spectrophotometer.
A suspension of p-tert-butylcalix[4]arene 4 (0.27 g,
0.41 mmol ) and CsF (0.31 g, 2.07 mmol) in dry CH3CN
(100mL)wasrefluxedfor1h.Thenasolutionoftosylated
TTF 3 (0.35 g, 0.41 mmol) in dry CH3CN (100 mL) was
slowly added over a 8 h period. The mixture was refluxed
for 24 h before the solvent was removed under reduced
pressure. The residue was dissolved in CH2Cl2 (30 mL)
and brine was added. The organic layer was separated
2.1.
Synthesis of 2,3-bis[2-(2-hydroxyethoxy)
ethylsulfanyl]-6,7-bis(methylthio)
tetrathiafulvalene (2) [17]
The TTF derivative 1 (1.13 g, 2.42 mmol) [18] was and dried over MgSO4. The crude product obtained
dissolved in THF (50 mL) and degassed with N2 for after evaporation of the solvent was purified on a silica
30 min. A solution of CsOH•H2O (0.88 mg, 5.32 mmol) column using methylene chloride/petroleum ether (2:1,
in dry methanol (2 mL) was added in one portion, V:V) to give 5 as orange powders in 36% yield. Mp:
1
producing a darkening of the solution. After stirring for 155-157ºC. H NMR (400 MHz, CDCl3, ppm): δ: 7.44
an additional 30 min, a solution of 2-(2-iodoethoxy) (s, 2 H, OH), 7.05 (s, 4 H, ArH), 6.83 (s, 4 H, ArH), 4.33
ethanol (3.14 g, 14.52 mmol) in THF (10 mL) was (d, J = 12.96 Hz, 4 H, ArCH2Ar), 4.12 (t, J = 4.6 Hz,
added. The reaction mixture was stirred for 24 h, and 4 H, ArOCH2), 4.06 (t, J = 4.5 Hz, 4 H, ArOCH2CH2), 3.94
the solvent was removed under reduced pressure. (t, J = 6.56 Hz, 4 H, OCH2CH2S), 3.30 (d, J = 13.00 Hz,
The resulting orange solid was dissolved in methylene 4 H, ArCH2Ar), 3.12 (t, J = 6.56 Hz, 4 H, OCH2CH2S),
chloride, washed with water several times, and dried 2.42 (s, 6 H, SCH3), 1.28 (s, 18 H, C(CH3)3), 0.98
over MgSO4. Concentration in vacuo and purification by (s, 18 H, C(CH3)3). 13C NMR (150 MHz, CDCl3): δ: 150.6,
a silicagel column chromatography (methylene chloride: 149.6, 147.0, 141.4, 132.8, 128.7, 127.8, 127.4, 125.9,
ethyl acetate = 2:1) afforded 2 as an orange solid 125.6, 125.1, 111.1, 110.6, 75.2, 70.2, 69.9, 38.2, 35.3,
in 45
%
yield. Mp: 57ºC (Lit. [17] mp 56oC). 33.9, 33.8, 31.7, 31.6, 31.4, 31.2, 31.0, 29.7, 29.2.
1H NMR (CDCl3, ppm): δ: 3.74 (br, s, 4 H, OCH2), 3.69 IR (KBr cm-1): υ: 3434.9, 2961.9, 2917.6, 2865.5, 1635.0,
(t, J = 6.0 Hz, 4 H, OCH2), 3.59 (t, J = 4.4 Hz, 4 H, 1485.5, 1362.7, 1200.7, 1123.3, 1094.6, 1052.2, 863.1,
OCH2), 3.05 (t, J = 6.0 Hz, 4 H, SCH2), 2.67 (br, s, 811.0, 774.4. MS-ESI: m/z calculated: 1148.34; found:
1
2 H, OH), 2.43(s, 6 H, SCH3). Lit. H NMR (CDCl3, 1148 (M+), 1281 (M+Cs)+. Anal. Calcd for C60H76S8O6,
ppm): δ: 3.72 (t, J = 4.0 Hz,4 H, OCH2), 3.67 (t, J = 6.0 C, 62.70; H, 6.67; S, 22.27. Found: C, 62.45; H, 6.84;
Hz, 4 H, OCH2), 3.56 (t, J = 4.0 Hz, 4 H, OCH2), 3.02 S, 22.14.
(t, J = 6.0 Hz, 4 H, SCH2), 2.40(s, 6 H, SCH3).
2.4. Crystallographic study
2.2.
Synthesis of 2,3-bis[2-(2-tosyloxyethoxy)
ethylsulfanyl]-6,7-bis(methylthio)
tetrathiafulvalene (3)
X-Ray data for 5: C62H79NO6S8, M = 1190.74 g mol-1,
Monoclinic, space group C2/c,
a = 52.33(4) Å,
b = 11.223(8) Å , c = 23.969 (17 Å, α = 90º,
β = 112.180(9) º, γ = 90º, V = 13037(16) Å3; Z = 8,
Dc =1.213 g cm-3, μ = 0.321 mm-1, F(000) = 5072, crystal
dimensions of 0.23×0.12×0.11 mm. The final refinement
To a solution of 2 (0.58 g, 1.09 mmol) in methylene
chloride (30 mL) was added tosyl chloride (0.46 g,
2.39 mmol). The solution was cooled to 0ºC and NEt3
1103