Supramolecular Insulating Networks Sheathing Conducting Nanowires Based on Organic Radical Cations (original) (raw)
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Chemistry of Materials, 2006
The procedure for 1a was employed, using decafluorobiphenyl (0.67 g, 2.0 mmol) as perfluoroarene. The light brown/yellow reaction mixture was quenched with H 2 O and extracted with hexanes (3 x 50 mL). The combined extract was dried over anhydrous MgSO 4 , filtered and evaporated to dryness. The resulting residue was subjected to column chromatography on alumina gel (hexane:diethyl ether) to give 225 mg (0.25 mmol, 50% yield) of 1b as a pale yellow powder. 2,5-Bis(nonafluorbiphenyl)-thiophene (2b). To a solution of 2,5-diiodothiophene (0.134 g, 0.4 mmol) in diethylether (30 mL) at-78 °C was added tert-butyllithium (1.0 mL, 1.5 M in hexanes) dropwise via syringe. This solution was allowed to warm up to room temperature over 5 h, resulting in a white suspension. This solution was then added dropwise to a solution of decafluorobiphenyl (550 mg, 1.6 mmol) in diethylether (75 mL) at-30 °C. The reaction mixture was allowed to warm to room temperature over 5 h. The resulting white suspension was quenched with water and the organics were extracted with CH 2 Cl 2. The extracts were dried over MgSO 4 and concentrated via rotary evaporation. The disubstitued product was isolated via sublimation to give 114 mg (0.16 mmol, 40 % yield) of 2b as small white needles. 2,5-Bis(heptafluoronapthyl)-thiophene (2c). To a solution of 2,5-diiodothiophene (0.134 g, 0.4 mmol) in diethylether (15 mL) at-78 °C was added tert-butyllithium (1.0 mL, 1.5 M in hexanes) dropwise via syringe. This solution was allowed to warm up to room temperature over 5 h, resulting in a white suspension. This suspension was diluted with hexanes (100 mL) then added dropwise to a solution of octafluoronapthalene (435 mg, 1.6 mmol) in hexanes (150 mL) at-30 °C. The reaction mixture was allowed to warm to room temperature over 10 h. The resulting dark yellow solution was quenched with water and the organics were extracted with toluene. The extracts were dried over MgSO 4 and concentrated via rotary evaporation. The disubstitued product was isolated via sublimation to give 60 mg (0.1 mmol, 25 % yield) of 2c as pale yellow flakes. 5,5'-Bis(nonafluorbiphenyl)-2,2'-bithiophene (3b). To a solution of 2,2'-bithiophene (0.083 g, 0.5 mmol) in dry THF (10 mL) was added butyllithium (0.55 mL, 1.6 M solution in hexanes) and the resulting white suspension was mixed for 1 h. The 5,5'dilithio-2,2'-bithiophene suspension was then added dropwise to a solution of excess decafluorobiphenyl (0.67 g, 2.0 mmol) in hexanes:THF (75:25) at-78 °C. The resulting mixture was allowed to warm to room temperature with stirring (9 h), and was then quenched H 2 O and extracted with CH 2 Cl 2. The mixture was filtered to remove large amounts of insoluble material, dried over anhydrous MgSO 4 , filtered over Celite and evaporated. The residue was purified via sublimation, to remove excess decafluorobiphenyl and the monosubstituted bi-product to give 190 mg (0.24 mmol, 47 % yield) of 3b as a bright yellow powder. 5,5'-Bis(heptafluoronapthyl)-2,2'-bithiophene (3c). To a solution of 2,2'-bithiophene (0.083 g, 0.5 mmol) in dry THF (10 mL) was added butyllithium (0.55 mL, 1.6 M solution in hexanes) and the resulting white suspension was mixed for 1 h. The 5,5'dilithio-2,2'-bithiophene suspension was then added dropwise to a solution of excess octafluoronapthalene (0.544 g, 2.0 mmol) in THF at-78 °C. The resulting mixture was allowed to warm to room temperature with stirring (9 h), and was then quenched H 2 O and extracted with CH 2 Cl 2. The product, insoluble in THF and CH 2 Cl 2 was isolated via filtration and washed with CH 2 Cl 2 to give 168 mg (0.25 mmol, 50 % yield) of 3c as a rust orange powder.
Inorganica Chimica Acta, 1988
The compounds of general formula [Ln(DMF)s-(WO~l(CF2Q)~ (Ln = La-Eu, Tb, Dy) were synthesized and characterized by microanalysis, conductance measurements, IR absorption (Nd3') and emission (Eu3+) spectra. The crystal structure of the neodymium compound was determined by X-ray diffraction techniques. The compound crystallizes in the triclinic system, space group PI, a = 8..589(4), b = 11.222(2), c = 12.271(2) A, Q = 56.83(2), fl= 62.13(2), y = 75.14(2)", V= 875.2 A', M= 918.4, Z= 1, D,=1.73 g cmW3, h(MoKct)=0.71073 A, /J= 1.65 mm-', F(OO0) = 456, R = 0.056, R, = 0.057, for 2979 independent reflections with I> 3a(o. Nd3+ is coordinated to the oxygen atoms of six independent water molecules at a mean distance Nd-0 = 2.52(l) A, and to the oxygen atoms of three independent DMF groups at a mean distance Nd-0 = 2.40(2) A. The coordination polyhedron is a tricapped trigonal prism of point symmetry C3,. was gently warmed, resulting in an oily product. Crystallization of the complexes was obtained by the diffusion method, using chloroform as the outer solvent. The crystals were dried in air, over filter paper.
Supporting Information Part I. Chemical Synthesis and Characterization General Procedures
All reagents were purchased from Sigma-Aldrich (St Louis, MO, USA) or Macrocyclics (Dallas, TX, USA) unless stated otherwise. Solvents were freshly distilled on appropriate driers and reactions run under an inert Argon atmosphere (CH 2 Cl 2 was distilled over P 2 O 5 , THF was distilled over sodium). All compounds apart from those containing Gd were fully characterized by 1 H (400 Hz) NMR, 13 C (400 Hz) (Bruker AMX-400 spectrometer) and the final products with Gd were characterized by mass spectrometry (EIMS and HRMS). Chemical shifts are expressed in δ ppm. All photophysical experiments were carried out using spectroscopic-grade solvents. Column chromatography was performed either over Silica Gel 60 (70-230 mesh) or neutral Alumina (Brockmann grade III, 50 mesh). UV-visible spectra were recorded on Varian Cary 50 Bio UV-visible spectrophotometer using CH 2 Cl 2 as solvent unless otherwise specified. Fluorescence spectra were recorded on a Varian Cary Eclipse fluorescence spectrophotometer with an excitation wavelength in the "Soret" band region between 410 and 425 nm.
Synthesis and characterization of volatile trifluoromethyl alkyl tellurides
Organometallics, 1992
Procedure for 2. Phosphetane 1 (0.096 g, 0.465 mmol) and methylene chloride (1.5 mL, 13.3 mmol) were syringed into a Teflon-screw-top pressure NMR tube (Wilmad). The tube was heated in an oil bath at 90 "C for 68 h. The reaction is quantitative by 31P NMR spectroscopy. X-ray-quality crystals were obtained by reacting 0.960 g (4.65 mmol) of the phosphetane with 0.5 mL (4.44 mmol) of CH2C12. Crystals formed upon heating at 90 "C overnight. A partial X-ray structure was determined for 2. However, due to the presence of isomers of 1, there was disorder in the structural determination. 31P(1H) NMR (200 MHz, CD,ClJ: 6 22.3 (8, tram,trarw9-2), 19.8 (AB quartet, cM,trarw-2), 17.3 (8, cis,cisd). The singlet peak aasignmenta were made by assuming that the cis isomer remains upfield of the trans isomer.
Incorporation of cis - and trans -4,5-Difluoromethanoprolines into Polypeptides
Organic Letters, 2012
Experimental details S43 Supplementary references S44 Abbreviations DIPEA diisopropylethylamine Np p-nitrophenyl-6-Cl-HOBt 6-cloro-N-hydroxybenzotriazole TBTU O-(Benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate S2 Materials and methods 1 Hand 13 C-NMR spectra were recorded on a Bruker Avance 300, a Bruker Avance 400, and a Bruker Avance 500 spectrometers as specified below and referenced to TMS. 19 F-NMR spectra were recorded on a Bruker Avance 300 spectrometer and referenced to trifluoroacetic acid in water (set to-75 ppm) as an external standard, the experiments were run without proton decoupling. Mass spectra were recorded on a Finnigan MAT90 (70 eV) spectrometer using electron impact (EI) ionization. Infra-red spectra were recorded on a Bruker ALPHA FT-IR spectrometer with a diamond-ATR module, only values above 1500 cm-1 are denoted. CHN-analysis was done on an Elementar vario MICRO cube analyzer. Optical rotation at 20 °C was analysed on a PerkinElmer 241 Polarimeter at 20°C. Melting points were measured on a Büchi 510 melting point apparatus (3 °/min scan) and are uncorrected. Matrix-assisted laser desorption/ionization with time-of-flight detection (MALDI-TOF) mass spectra were recorded on a Bruker Autoflex III instrument. Reverse-phase high-performance liquid chromatography (RP-HPLC) was performed on a Jasco HPLC system with PU-2080 Plus pumps and a diode-array UV-detector. Vydac polymeric C18 columns were employed (4.6 mm x 250 mm as analytical (flow rate 1.5 mL/min), 10 mm x 250 mm as semi-preparative (6 mL/min) and 22 mm x 250 mm as preparative (20 mL/min)). Linear gradients, using as solvent A: 90% water, 10% acetonitrile, solvent B: 90% acetonitrile, 10% water; 5 mM hydrochloric acid was used as an ion-pairing agent in all cases i. Tetrahydrofuran (THF), diglyme, DIPEA, and diethyl ether were freshly distilled under a nitrogen atmosphere from sodium/benzophenone. Toluene was distilled from sodium. Trifluoroacetic anhydride was distilled over dry potassium carbonate. All other chemicals were of appropriate commercial grades (purchased from Merck, Acros, ABCR, Fisher, Iris Biotech, Biosolve) and used without further purification unless otherwise stated. Experimental procedures Methyl (S)-5-Oxo-pyrrolidine-2-carboxylate (Pyr-OMe, S1) N H O CO 2 Me The compound was prepared using the modified literature protocol. ii (S)-Pyroglutamic acid 5 (33 g, 0.26 mol) was dissolved in methanol (HPLC grade, 1 L); thionyl chloride (2.5 mL, 0.03 mol) was added dropwise upon stirring under argon within 1 min. The solution was kept S3 stirred at room temperature for 16 h. Saturated sodium carbonate solution was added until pH ~7. Methanol was removed under reduced pressure. The product was taken up in dichloromethane (250 mL), washed with brine (100 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure giving 29.75 g (81% yield) of the product as a pale yellow oil which was used in the next step without any further purification. 1-tert-Butyl 2-methyl (S)-5-Oxo-pyrrolidine-1,2-dicarboxylate (Boc-Pyr-OMe, S2) N O CO 2 Me Boc The synthetic procedure published in iii was used, starting from Pyr-OMe (S1). The crude Boc-Pyr-OMe (S2) was purified by silica gel column chromatography, eluting with dichloromethane:diethyl ether (gradient from 5:0 to 3:2). 30.6 g of the product was obtained starting from 20 g of Pyr-OMe (90% yield). The measured [α] D =-30.7° (CHCl 3 , c = 0.47) was consistent with the value-30.4° (CHCl 3 , c = 1.00) reported in the literature. iv 1 H-NMR (400 MHz, DMSO-d 6) δ, ppm: 4.62 (dd, J = 9, 3 Hz, 1H), 3.72 (s, 3H), 2.45 (m, 2H), 2.31 (m, J = 13, 3 Hz, 1H), 1.90 (m, J = 4 Hz, 1H), 1.40 (s, 9H). 1-tert-Buthyl 2-methyl (S)-2-pyrrolin-1,5-dicarboxylate (Boc-DhPro-OMe, 4) N CO 2 Me Boc The compound was synthesized according to the published protocol. v 7.80 g of the product was obtained from 10 g of starting S2 (83% yield). 1 H-NMR (CDCl 3 , 400 MHz)-(rotamers, 10:9, δ, ppm): 6.65 and 6.52 (two m, 1H, N-CH=CH), 4.96 and 4.91 (two m, 1H, N-CH=CH), 4.66 and 4.59 (two dd, J= 12, 5Hz, 1H, CH-CO 2 Me), 3.76 (s, 3H, CO 2 CH 3), 3.06 (m, 1H, CHH), 2.67 (m, 1H, CHH), 1.49 and 1.44 (two s, 9H, C(CH 3) 3). 2-tert-butyl 3-methyl (1S,3S,5R)-6,6-difluoro-2-azabicyclo[3.1.0]hexane-2,3dicarboxylate (Boc-trans-4,5-F 2 MePro-OMe, trans-6) N CO
Patnaik P. Handbook of inorganic chemicals (MGH, 2003)(T)(1125s)
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