An electron-rich three dimensional receptor based on a calixarene- tetrathiafulvalene assembly
J. Lyskawa, D. Canevet, M. Allain, M. Sallé*
Institut des Sciences et Technologies Moléculaires d'Angers, Moltech Anjou, Université d'Angers, CNRS UMR 6200,2 Boulevard Lavoisier, 49045 Angers, France
Email: marc.salle@univ-angers.fr
Compound 3: Synthesis, 1H and 13C NMR spectra Page 2
Compound 4: Synthesis, 1H and 13C NMR spectra Page 4
Compound 1b: Synthesis, 1H and 13C NMR spectra Page 5
X-Ray crystallography details Page 6
Cyclic voltammetry study: Calixarene 1b titration with lithium perchlorate Page 7
Spectroscopic data were obtained with the equipment facilities of the PIAM (technical platform) at the University of Angers. 1H-NMR (500.13 MHz) and 13C-NMR (125.75 MHz) spectra were recorded on a BRUKER Advance DRX 500 spectrometer.
Chemical shifts (δ) are expressed in ppm related to the tetramethylsilane (TMS) signal and J values are in Hz. Mass spectra were achieved on a JEOL JMS 700 B/ES for high resolution measurements. Cyclic voltammetry experiments were carried out on a potentiostat- galvanostat EG&G PARK models 273 or 273A, with solvents and electrolytes of electrochemical grades.
Compound 3. Chloroacetyl chloride (160 µ L – 1.98 mmol – 1.5 eq.) was slowly added to a solution of hydroxymethyltetrathiafulvalene 2 (310 mg – 1.3 mmol) and triethylamine (400 µ L – 2.88 mmol – 2.2 eq.) in dry dichloromethane (25 mL). The mixture was stirred for three hours and concentrated in vacuo. The desired compound was isolated by silica gel chromatography (CH2Cl2 / petroleum ether = 8 / 2) as a yellow solid (80 %). 1H NMR (Acetone-D6): 6.74 (s, 1H, Hc), 6.59 (s, 2H, Ha,b), 4.99 (s, 2H, Hd), 4.33 (s, 2H, He); 13C NMR (Acetone-D6): 167.6 (-CO2-), 131.2, 121.6, 120.3, 120.2 (TTF external C=C), 112.4, 109.2 (TTF central C=C), 62.5 (-CH2O-), 41.3 (-CH2Cl).
Compound 4. A mixture of sodium iodide (3.0 g – 20 mmol – 30 eq.) and chlorinated compound 3 (210 mg – 0.68 mmol) was refluxed overnight under inert atmosphere. Solvent was evaporated under reduced pressure and the desired iodinated derivative 4 was isolated by silica gel chromatography (CH2Cl2 / petroleum ether / NEt3 = 180 / 69 /1) as a yellow solid (96 %). 1H NMR (Acetone-D6): 6.81 (s, 1H, Hc), 6.64 (s, 2H, Ha,b), 4.96 (s, 2H, Hd), 3.85 (s, 2H, He); 13C NMR (Acetone-D6): 169.2 (-CO2-), 131.3, 121.5, 120.3, 120.2 (TTF external C=C), 112.0, 109.0 (TTF central C=C), 62.4 (-CH2O-), -5.3 (-CH2I).
Compound 1b. Calixarene 5 (150 mg – 0.17 mmol), dicyclohexylcarbodiimide (140 mg - 0.68 mmol – 4 eq.), N,N-dimethylaminopyridine (83 mg – 0.68 mmol – 4 eq.) and 1- hydroxybenzotriazole (93 mg – 0.68 mmol – 4 eq.) were successively added in dry dichloromethane (15 mL). The resulting mixture was stirred for 15 minutes at room temperature and alcohol 2 (160 mg – 0.68 mmol – 4 eq.) was added. After stirring 24 hours under inert atmosphere, the white precipitate (DCU) was removed by filtration and dichloromethane was added (100 mL). The resulting solution was washed with water, dried over magnesium sulfate and concentrated in vacuo. A recrystallization from CH2Cl2 and methanol allowed isolation of 1b in a 60 % yield. Mp. 108-110°C, 1H NMR (Acetone-D6):
6.89 (s, 8H, Hg,h), 6.69 (s, 4H, Ha), 6.60 (d, J = 6.5 Hz, 4Hb/c), 6.58 (d, J = 6.5 Hz, 4H, Hc/b) 5.04 (s, 8H, Hd), 4.89 (s, 8H, He), 4.87 (d, JAB = 13.0 Hz, 4H, Hf), 3.24 (d, JAB = 13.0 Hz, 4H, Hf), 1.10 (s, 36H, Hi); 13C NMR (Acetone-D6): 170.59 (C=O), 153.94 (Ar ipso), 145.84 (Ar para), 134.37 (Ar ortho), 132.10 (Ar meta), 126.27, 120.78, 120.40, 120.27 (TTF peripheral C=C), 112.10. 109.54 (TTF central C=C), 71.87 (CH2C=O), 61.52 (TTFCH2O-), 34.43 (C(Me)3), 32.56 (ArCH2Ar), 31.74 (tBu). MS (HR): (M + Na)+. Calc.: 1769.108; Exp. : 1769.105.
X-Ray crystallography
X-ray single-crystal diffraction data were collected at 293K on a BRUKER-NONIUS KappaCCD diffractometer, equipped with a graphite monochromator utilizing MoKα radiation (λ = 0.71073Å). The structure was solved by direct methods using SIR92 (Altomare et al.,1993) and refined on F2 by full matrix least-squares techniques using SHELXL97 (G.M.
Sheldrick, 1998). All non-H and non-C atoms were refined anisotropically and absorption was corrected by SADABS program (Sheldrick, Bruker, 2000). The H atoms were included in the calculation without refinement.
Crystallographic data for 1b : C81.5H83Cl3F6Na1O12P1S16, M = 2041.75, yellow needle, 0.60 x 0.12 x 0.09 mm3, monoclinic, space group P21/c, a = 16.68(2) Å, b = 29.95(5) Å, c = 19.94(2) Å, β = 93.50(7)°, V = 9946(23) Å3, Z = 4, ρcalc = 1.364 g/cm3, µ(MoKα) = 0.513 mm-1, F(000) = 4220, θmin = 3.03°, θmax = 21.42°, 41756 reflections collected, 11005 unique (Rint
= 0.13), parameters / restraints = 689 / 0, R1 = 0.1401 and wR2 = 0.3493 using 4186 reflections with I>2σ(I), R1 = 0.2942 and wR2 = 0.4255 using all data, GOF = 1.173, -0.482
< ∆ρ < 1.013 e.Å-3. CCDC-780590 contains the supplementary crystallographic data for this paper
Evolution of 1b cyclic voltammogram upon addition of lithium perchlorate;
[1b] = 5.10-4 mol/L, TBAPF6 0.1M, v = 100 mV/s vs. Ag/AgCl, Acetonitrile / CH2Cl2 (1 / 1), Pt, ∅ = 1.6 mm.
