Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes

• Sara J. Krivickas,
• Chiho Hashimoto,
• Junya Yoshida,
• Akira Ueda,
• Kazuyuki Takahashi,
• John D. Wallis and
• Hatsumi Mori

Beilstein J. Org. Chem. 2015, 11, 1561–1569, doi:10.3762/bjoc.11.172

• ,S)-2. The other enantiomer (R,R)-2 was synthesized in the same manner. The cyclic voltammetry measurement on racemic-1 indicated the first and second oxidation potentials (E11/2, E21/2) and their difference ΔE (= E21/2 − E11/2) to be 0.52, 0.83, and 0.31 V by utilizing glassy carbon as working

• ) spectra were measured with a JEOL JNM-AL300 spectrometer with CDCl3 as solvent using Me4Si or residual solvent as an internal standard. Cyclic voltammetry (CV) measurements were performed on an ALS 610DB electrochemical analyzer in benzonitrile containing 0.1 M tetrabutylammonium perchlorate (working

Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

• Awatef Ayadi,
• Aziz El Alamy,
• Olivier Alévêque,
• Magali Allain,
• Nabil Zouari,
• Mohammed Bouachrine and
• Abdelkrim El-Ghayoury

Beilstein J. Org. Chem. 2015, 11, 1379–1391, doi:10.3762/bjoc.11.149

• external ethylenic atom of the TTF moiety which is confirming the good electronic conjugation in this ligand. The same behavior is observed for the TTF pyridine carboxaldehyde precursors 1 and 2 (Figure S3, Supporting Information File 1). Cyclic voltammetry The electrochemical behavior of the electroactive

• precursors 1 and 2 as well as of ligands L1 and L2 was investigated by cyclic voltammetry (Figure 6 and Table 3). The measurements in the case of precursors 1 and 2 show two reversible oxidations at E1ox = +0.26 V, E2ox = +0.75 V and E1ox = +0.32 V, E2ox = +0.77 V vs Ag/Ag+, respectively, that are anodically

• quartz cuvettes using Perkin Elmer spectrophotometer. Mass spectra were collected with Bruker Biflex-III TM. IR spectra were recorded on a Bruker vertex 70. Elemental (C, H and N) analyses were performed on a Thermo-Scientific Flash 2000 Organic Elemental Analyzer. Cyclic voltammetry (CV) experiments

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• have reported the synthesis of ethylene-bridged phenothiazinophane 92 using the McMurry coupling reaction. Also cyclic voltammetry experiments indicated the intramolecular electronic communication between the phenothiazinyl subunits. Calixarene-based macrocycles bind with various metal ions. Lee and

Cathodic hydrodimerization of nitroolefins

• Michael Weßling and
• Hans J. Schäfer

Beilstein J. Org. Chem. 2015, 11, 1163–1174, doi:10.3762/bjoc.11.131

• reduction of 1-nitroalkenes was studied by cyclic voltammetry and controlled potential coulometry. The reduction probably proceeds by initial formation of the radical anion, which subsequently dimerizes [17]. Later conditions were described to achieve selectively either a cathodic ß,ß-coupling (cathodic

• hydrodimerization is performed in a divided electrolysis cell by variation of the electrolyte (Table 1, Scheme 2). The working potential was chosen from cyclic voltammetry and current/voltage curves in the cell used for the preparative conversion. The potential in the controlled potential electrolysis was −0.9 V to

• derived. Cyclic voltammetry The reduction potentials (Ep,c) of the nitroalkenes were determined by cyclic voltammetry. The values, ordered by decreasing potentials, are shown in Scheme 4. The reduction potentials Ep,c are determined by the conformation of the aryl group, the electron density at the double

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene: the effect of planarisation on charge transport properties

• Rupert G. D. Taylor,
• Joseph Cameron,
• Iain A. Wright,
• Neil Thomson,
• Olena Avramchenko,
• Alexander L. Kanibolotsky,
• Anto R. Inigo,
• Tell Tuttle and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1148–1154, doi:10.3762/bjoc.11.129

• and electrochemical properties of compounds 1 and 2 have been measured by UV–vis spectroscopy and cyclic voltammetry and the results compared with density functional theory (DFT) calculations to confirm the observed properties. Organic field effect transistor (OFET) devices fabricated from 1 and 2

• charge transfer (CT) from the TTF to the electron-deficient thiazole units, facilitated due to their planarity. The structural properties of each compound will be expanded upon in the theoretical calculations section. Solution-state cyclic voltammetry was employed to determine the highest occupied

• the synthesis of a half-unit and a final triethyl phosphite mediated homo-coupling. The resultant compounds, 1 and 2, were fully characterised and their optical and electrochemical properties elucidated via UV–vis spectroscopy and cyclic voltammetry, and explained in conjunction with DFT level

New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries

• Shintaro Iwamoto,
• Yuu Inatomi,
• Daisuke Ogi,
• Satoshi Shibayama,
• Yukiko Murakami,
• Minami Kato,
• Kazuyuki Takahashi,
• Kazuyoshi Tanaka,
• Nobuhiko Hojo and
• Yohji Misaki

Beilstein J. Org. Chem. 2015, 11, 1136–1147, doi:10.3762/bjoc.11.128

• –680 mAh g−1. The discharge capacities after 40 cycles were 64–86% of the initial discharge capacities. Keywords: cyclic voltammetry; positive electrode materials; rechargeable battery; redox; tetrathiafulvalene; Introduction Tetrathiafulvalene (TTF, 1a) and its analogues have attracted much

• HOMO–2 of TTPY (−5.439 eV). These results suggest that the electrons at the HOMO–2 of 5a and 6a and HOMO–4 of 8a might be removed more easily than those at the HOMO–2 of TTPY. Electrochemical properties The redox behaviors of 5d, 7d and 9d were investigated by using cyclic voltammetry. Deconvoluted

• the full discharge capacity reached in 5 h. Cyclic voltammetry in the solid state was carried out prior to the charge–discharge test so as to determine the turning back voltage (Supporting Information File 1, Figure S4). The electrodes incorporating 5b and 5c exhibited three indistinct oxidation peaks

Regioselective synthesis of chiral dimethyl-bis(ethylenedithio)tetrathiafulvalene sulfones

• Flavia Pop and
• Narcis Avarvari

Beilstein J. Org. Chem. 2015, 11, 1105–1111, doi:10.3762/bjoc.11.124

• conformation. Cyclic voltammetry measurements indicate fully reversible oxidation in radical cation and dication species. Keywords: chirality; crystal structures; molecular materials; sulfones; tetrathiafulvalenes; Introduction Chiral tetrathiafulvalene (TTF) derivatives have been addressed for the first

• generated lose oxygen to afford BEDT-TTF. However, in strike contrast with the behavior of the latter, cyclic voltammetry measurements for (R,R)-1 and (S,S)-1 show reversible two single-electron oxidation processes into radical cation and dication species at ΔE1/2 = +0.67 and 1.00 V vs SCE, respectively

• . Electrochemical studies: Cyclic voltammetry measurements were carried out with a Biologic SP-150 potentiostat in a glove box containing dry, oxygen-free (<1 ppm) argon at 293 K, by using a three-electrode cell equipped with a platinum millielectrode of 0.126 cm2 area, an Ag/Ag+ pseudo-reference electrode and a

Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F₄TCNQ

• Raúl García,
• M. Ángeles Herranz,
• Edmund Leary,
• M. Teresa González,
• Gabino Rubio Bollinger,
• Marius Bürkle,
• Linda A. Zotti,
• Yoshihiro Asai,
• Fabian Pauly,
• Juan Carlos Cuevas,
• Nicolás Agraït and
• Nazario Martín

Beilstein J. Org. Chem. 2015, 11, 1068–1078, doi:10.3762/bjoc.11.120

• carbonyl groups appear at 192.4 ppm and the carbons of the alkyne moieties at 88.0 and 90.4 ppm, with the terminal methyl groups at 28.7 ppm. The redox properties of compound 5 (0.2 mM) were determined by cyclic voltammetry at room temperature in THF using TBAPF6 (0.1 M) as a supporting electrolyte under

A hybrid electron donor comprising cyclopentadithiophene and dithiafulvenyl for dye-sensitized solar cells

• Gleb Sorohhov,
• Chenyi Yi,
• Michael Grätzel,
• Silvio Decurtins and
• Shi-Xia Liu

Beilstein J. Org. Chem. 2015, 11, 1052–1059, doi:10.3762/bjoc.11.118

• conduction band and the dye regeneration, the corresponding electrochemical and photophysical properties were investigated. As depicted in Figure 2, cyclic voltammograms of dyes 1 and 2 in CH2Cl2 show two reversible oxidation waves. To gain additional insight into the redox processes, the cyclic voltammetry

• , multiplet. HRMS data were obtained with electrospray ionization (ESI). Cyclic voltammetry was performed in a three-electrode cell equipped with a platinum-disk working electrode, a glassy carbon counter electrode, and Ag/AgCl was used as the reference electrode. The electrochemical experiments were carried

Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

• Yoann Cotelle,
• Marie Hardouin-Lerouge,
• Stéphanie Legoupy,
• Olivier Alévêque,
• Eric Levillain and
• Piétrick Hudhomme

Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115

• molecular clips 1–4 were determined using cyclic voltammetry experiments (Table 2). These studies displayed a different electrochemical behavior for clips 1, 2 and 3 in comparison to clip 4. In the latter case, the cyclic voltammogram (CV) showed two oxidation waves at Eapp0ox1 = +0.28 V and Eapp0ox2

• molecular clip using the N-tetraalkylation of glycoluril constitutes a powerful versatile method allowing an easy access to new architectures for which electrochemical properties can be tuned by simple modification of peripheral substituents on the TTF moiety. Cyclic voltammetry and spectroelectrochemical

Chiroptical properties of 1,3-diphenylallene-anchored tetrathiafulvalene and its polymer synthesis

• Masashi Hasegawa,
• Junta Endo,
• Seiya Iwata,
• Toshiaki Shimasaki and
• Yasuhiro Mazaki

Beilstein J. Org. Chem. 2015, 11, 972–979, doi:10.3762/bjoc.11.109

• . cyclic voltammetry (CV) measurements were performed on Hokuto Denko HZ-5000 electrochemical analyzer. GPC analysis for the polymer products was carried out at 40 °C on a Shodex GPC apparatus equipped with two SB-806M HQ GPC columns (Showa Denko K. K.) and a UV detector. DMF was used as the eluent at a

• . Moreover, the ECD intensities of both enantiomers did not change under ambient light, at least over several days. Therefore, 1,3-diphenylallene is a reliable chiral source for a chiral polymer having electron-donating units. The electrochemical properties of 3 and PTDPA were investigated by cyclic

• voltammetry (CV) analyses (Figure 4 and Table 1). In CVs, there are two sets of reversible redox waves in the conventional potential range. Compound 3 exhibits two two-electron transfer waves at E11/2 = −0.01 V and E21/2 = 0.31 V, whereas PTDPA exhibits in a similar manner at E11/2 = 0.03 V and E21/2 = 0.30 V

Tuning the size of a redox-active tetrathiafulvalene-based self-assembled ring

• Sébastien Bivaud,
• Sébastien Goeb,
• Vincent Croué,
• Magali Allain,
• Flavia Pop and
• Marc Sallé

Beilstein J. Org. Chem. 2015, 11, 966–971, doi:10.3762/bjoc.11.108

• the free ligand L1 (35° and 63°). By comparison, the pyridyl units in complex M4L2 are tilted with angles of 52° and −69° in the solid (Figure 4a). Those higher values result from the increased steric demand generated by the dppf coligand. A cyclic voltammetry study of prism M6L3 was carried out in

Carboxylated dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, electronic properties, and complexation with zinc ions

• Yunfei Wang and
• Yuming Zhao

Beilstein J. Org. Chem. 2015, 11, 957–965, doi:10.3762/bjoc.11.107

• properties of the coordination polymer were investigated by infrared spectroscopy, cyclic voltammetry, powder X-ray diffraction, and differential scanning calorimetric analyses. Furthermore, the microscopic porosity and surface area of the Zn-TTFV coordination polymer were measured by nitrogen gas adsorption

• in these molecules are still retained at a similar level in the ground state. The electrochemical redox properties of compounds 4–9 were characterized by cyclic voltammetry, and the detailed cyclic voltammograms are shown in Figure 2. For methyl ester-appended DTF 4 (Figure 2A) an anodic peak was

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

• Sandrina Oliveira,
• Dulce Belo,
• Isabel C. Santos,
• Sandra Rabaça and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 951–956, doi:10.3762/bjoc.11.106

• voltammetry, NMR, UV-visible and IR spectroscopy. Keywords: cross-coupling; cyanobenzene; cyclic voltammetry; dissymmetric tetrathiafulvalene; electro-active donors; Introduction The tetrathiafulvalene molecule (TTF) and its many derivatives, due to its unique π-donor properties, have been at the basis of

• . The redox properties of this donor were studied by cyclic voltammetry in dichloromethane using [n-Bu4N][PF6] as the supporting electrolyte (Figure 4) showing two one-electron quasi-reversible redox waves at 0.405 V and 0.850 V vs Ag/AgNO3 as typical of TTF donors, which are ascribed to the couples

• as solvents respectively and TMS the internal reference. UV–vis spectra were recorded on an UV-1800 Shimadzu spectrophotometer. Cyclic voltammetry data were obtained using a BAS C3 Cell Stand. The voltammograms were obtained at room temperature with a scan rate of 100 mV/s, platinum wire working and

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

• Huixin Jiang,
• Virginia Mazzanti,
• Christian R. Parker,
• Søren Lindbæk Broman,
• Jens Heide Wallberg,
• Karol Lušpai,
• Adam Brincko,
• Henrik G. Kjaergaard,
• Anders Kadziola,
• Peter Rapta,
• Ole Hammerich and
• Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2015, 11, 930–948, doi:10.3762/bjoc.11.104

• were investigated by cyclic voltammetry, UV–vis–NIR and EPR absorption spectroscopical methods of the electrochemically generated oxidized species. The electron-accepting properties of the acetylenic cores were also investigated electrochemically. Keywords: alkynes; mixed valence; radiaannulene

• -conjugated tetraethynylethene (TEE) spacer as in compound 1a (Figure 1), then the two TTFs behave as independent redox centres that are oxidized at the same potentials in cyclic voltammetry (two two-electron oxidations) [8][9][10]. However, by bridging the two TTFs with an additional TEE in a cyclic

• structure, as in the radiaannulene 2a, communication between the two TTFs is observed in the cyclic voltammetry experiment, and the first two-electron event showed the waves diverging from each other (two stepwise oxidations) [10]. In addition, the intermediate radical cation showed an IVCT absorption at

Tuning of tetrathiafulvalene properties: versatile synthesis of N-arylated monopyrrolotetrathiafulvalenes via Ullmann-type coupling reactions

• Vladimir A. Azov,
• Diana Janott,
• Dirk Schlüter and
• Matthias Zeller

Beilstein J. Org. Chem. 2015, 11, 860–868, doi:10.3762/bjoc.11.96

• direct conjugation with the tetrathiafulvalene chromophore. The crystal packing of the arylated monopyrrolotetrathiafulvalenes is primarily defined by networks of C–H···X weak hydrogen bonds and short S···S contacts involving the tetrathiafulvalene moieties. Keywords: cyclic voltammetry; N-arylation

• aromatic MPTTF conjugates were determined using cyclic voltammetry (CV) in CH2Cl2/Bu4NClO4 solution and are summarized in Table 1. The CVs of all compounds displayed two reversible oxidation waves on the cathodic scan (Figure 4) characteristic to TTFs [1], the first one leading to the radical cation and

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• will be described, based on the X-ray crystal structure analyses of four neutral TTF derivatives, i.e., the EDT-TTF derivatives 2ac and 2bc and the tetrasubstituted derivatives 3bc and 4bc. Redox properties Cyclic voltammetry was used to evaluate the evolution of the donor strength with the nature and

TTFs nonsymmetrically fused with alkylthiophenic moieties

• Rafaela A. L. Silva,
• Bruno J. C. Vieira,
• Marta M. Andrade,
• Isabel C. Santos,
• Sandra Rabaça,
• Dulce Belo and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 628–637, doi:10.3762/bjoc.11.71

• -ylidene)-1,3-dithiole-4,5-diyl]bis[sulfanediyl]}dipropanenitrile (α-mtdt, 2), were synthesized and characterized. The electrochemical properties of these electronic donors were studied by cyclic voltammetry (CV) in dichloromethane. Both compounds show two quasi-reversible oxidation processes, versus Ag

• /AgCl, typical of TTF donors at E11/2 = 279 V and E21/2 = 680 V for 1 and E11/2 = 304 V and E21/2 = 716 V in the case of 2. The single-crystal X-ray structure of 1 and of a charge transfer salt of 2, (α-mtdt)[Au(mnt)2] (3), are reported. Keywords: cyclic voltammetry; single-crystal X-ray diffraction

• charge transfer salt of 2, (α-mtdt)[Au(mnt)2] (3), (mnt = maleonitriledithiolate) could be obtained by electrocrystallization using standard conditions. Redox properties The redox properties of the donors 1 and 2 in solution were studied by cyclic voltammetry and the results are collected in Table 1

Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation

• Martin Weiser,
• Sergej Hermann,
• Alexander Penner and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2015, 11, 568–575, doi:10.3762/bjoc.11.62

• photoirradiation by both sunlight and green light-emitting diodes. Furthermore, based on Ered(PDI/PDI●−) = −0.28 V (measured by cyclic voltammetry, vs SCE, see Supporting Information File 1) and E00 = 2.35 eV (see Supporting Information File 1), PDI is an electron deficient chromophore with an excited state

Bis(vinylenedithio)tetrathiafulvalene analogues of BEDT-TTF

• Erdal Ertas,
• İlknur Demirtas and
• Turan Ozturk

Beilstein J. Org. Chem. 2015, 11, 403–415, doi:10.3762/bjoc.11.46

• was obtained in a similar manner. The redox properties of the donor molecules 29a–d, 32a–d, 33a–c and ET 3 were studied by cyclic voltammetry in solution in acetonitrile, containing NaClO4 and dichloromethane, containing tetrabutylammonium tetrafluoroborate (TBABF4) (Table 2 and Table 3). Measurements

• Table 4. The oxidation and reduction properties of the diphenyl analogues 56, 69 and 71 and monophenyl analogues 68a–c, 31a and 29a were investigated and compared by cyclic voltammetry (CV) (Table 5) with ET 3 and its fully unsaturated tetraphenyl analogue 52. The CV measurement of the donors was

Electrochemical oxidation of cholesterol

• Jacek W. Morzycki and
• Andrzej Sobkowiak

Beilstein J. Org. Chem. 2015, 11, 392–402, doi:10.3762/bjoc.11.45

• . However, the yields of the products were not reported. Based on cyclic voltammetry and rotating ring-disk electrode measurements the authors suggested that Br− is electrochemically oxidized through Br to BrO− and that the latter is the oxidizing agent for cholesterol. The oxidation of cholesterol by

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf₂N ionic liquid

• Andrea P. Sandoval,
• Marco F. Suárez-Herrera and
• Juan M. Feliu

Beilstein J. Org. Chem. 2015, 11, 348–357, doi:10.3762/bjoc.11.40

• , E-03080 Alicante, Spain 10.3762/bjoc.11.40 Abstract Thin films of PEDOT synthesized on platinum single electrodes in contact with the ionic liquid 1-ethyl-2,3-dimethylimidazolium triflimide ([EMMIM]Tf2N) were studied by cyclic voltammetry, chronoamperometry, infrared spectroscopy and atomic force

• electrochemical synthesis of PEDOT. The electrochemical properties of thin films of PEDOT are subsequently studied and compared with the behavior obtained in acetonitrile. Results and Discussion Cyclic voltammetry Figure 1 shows the cyclic voltammograms of EDOT in [EMMIM]Tf2N. The onset of the EDOT oxidation

• on platinum single crystal electrode substrates in [EMMIM]Tf2N. Cyclic voltammetry shows that the polymer grows faster in Pt(111) than in Pt(110) or Pt(100). On the other hand, the chronoamperometric experiments show that the activation energy for the oxidation and reduction processes is very low and

Functionalized branched EDOT-terthiophene copolymer films by electropolymerization and post-polymerization “click”-reactions

• Miriam Goll,
• Adrian Ruff,
• Erna Muks,
• Felix Goerigk,
• Beatrice Omiecienski,
• Ines Ruff,
• Rafael C. González-Cano,
• Juan T. Lopez Navarrete,
• M. Carmen Ruiz Delgado and
• Sabine Ludwigs

Beilstein J. Org. Chem. 2015, 11, 335–347, doi:10.3762/bjoc.11.39

• modification over the whole film. The integrity of the redox and optical behavior upon modification of the P(EDOT-N3-co-3T)-1:1 with sulfonic acid with regard to the parent copolymer was further proven by cyclic voltammetry and in situ spectroelectrochemistry. It was recently demonstrated that the azide group

Highly selective electrochemical fluorination of dithioacetal derivatives bearing electron-withdrawing substituents at the position α to the sulfur atom using poly(HF) salts

• Bin Yin,
• Shinsuke Inagi and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2015, 11, 85–91, doi:10.3762/bjoc.11.12

• derivatives (dithioacetals) were prepared, and their oxidation potentials () were measured by cyclic voltammetry in an anhydrous acetonitrile (MeCN) solution containing n-Bu4NBF4 (0.1 M) using a platinum disk working electrode and a saturated calomel electrode (SCE) as the reference electrode. All compounds

A facile synthesis of functionalized 7,8-diaza[5]helicenes through an oxidative ring-closure of 1,1’-binaphthalene-2,2’-diamines (BINAMs)

• Youhei Takeda,
• Masato Okazaki,
• Yoshiaki Maruoka and
• Satoshi Minakata

Beilstein J. Org. Chem. 2015, 11, 9–15, doi:10.3762/bjoc.11.2

• electronegative diazene (–N=N–) moiety, diazahelicenes 2 are expected to possess stabilized LUMO energies. The LUMO energies, which were estimated from cyclic voltammetry (CV) experiments [ELUMO = –(4.8 + redE1/2) eV] using diluted CH2Cl2 solutions (10−4 M) of 2, range from –2.92 to –3.13 eV (for the full cyclic