Star-shaped and linear π-conjugated oligomers consisting of a tetrathienoanthracene core and multiple diketopyrrolopyrrole arms for organic solar cells

• Hideaki Komiyama,
• Chihaya Adachi and
• Takuma Yasuda

Beilstein J. Org. Chem. 2016, 12, 1459–1466, doi:10.3762/bjoc.12.142

• LUMO energy levels were calculated to be –3.72 and –3.75 eV for TTA-DPP4 and TTA-DPP2, respectively. Because of their deep-lying HOMO levels and sufficient LUMO offsets (>0.5 eV), both TTA-DPP4 and TTA-DPP2 can serve as electron-donor materials in combination with [6,6]-phenyl-C71-butyric acid methyl

• ester (PC71BM) as an acceptor materials, which has a LUMO level of –4.3 eV. Photovoltaic properties The photovoltaic properties of TTA-DPP4 and TTA-DPP2 were also evaluated. BHJ-OSCs were fabricated using TTA-DPP4 and TTA-DPP2 as electron-donor materials and PC71BM as an electron-acceptor material, with

The synthesis of functionalized bridged polycycles via C–H bond insertion

• Jiun-Le Shih,
• Po-An Chen and
• Jeremy A. May

Beilstein J. Org. Chem. 2016, 12, 985–999, doi:10.3762/bjoc.12.97

• intramolecular C–H bond insertions to form monocyclic and fused bicyclic rings [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59]. The stronger the electron donor, the greater the observed insertion at the C–H bond on the carbon with that donor. For example

Separation and identification of indene–C₇₀ bisadduct isomers

• Bolong Zhang,
• Jegadesan Subbiah,
• David J. Jones and
• Wallace W. H. Wong

Beilstein J. Org. Chem. 2016, 12, 903–911, doi:10.3762/bjoc.12.88

• a number of advantages, such as lightweight flexible devices and low-cost fabrication using roll-to-roll printing [1]. Bulk-heterojunction organic solar cells (BHJ OSC) are a specific type of OSCs which contain a blend of organic electron donor and acceptor materials as the photoactive component

• increasing crystallinity of IC70BA can improve the charge carrier mobility of the bulk material but the miscibility with the P3HT electron donor material can also change. A key feature of efficient BHJ solar cell devices is the nanoscale phase separation of the electron donor and acceptor materials into

• electron donor and an electron acceptor) with the film nanostructure being extremely important for the device performance. Molecular structure of IC60BA and IC70BA. a) Schlegel diagram of C70; b) illustrations of three regioisomers of IC70BA and their geometrical isomers. Chromatograms of IC70BA mixture

Self and directed assembly: people and molecules

• Tony D. James

Beilstein J. Org. Chem. 2016, 12, 391–405, doi:10.3762/bjoc.12.42

• collaborate and in particular we worked together to improve the chiral discriminating systems. In order to improve the chiral systems we designed sensors using a d-PET rather than the normal a-PET fluorescence sensing mechanism. With d-PET systems the fluorophore is the electron donor and the protonated amine

• for acidic guests such as tartaric acid and sugar acids [62][63][64][65] (Figure 11). The best chiral discriminating d-PET system was constructed using a phenothiazine fluorophore 17 and 18 [66]. The phenothiazine fluorophore was chosen because it is a very strong electron donor. These sensors

Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

• Carmen Mejuto,
• Beatriz Royo,
• Gregorio Guisado-Barrios and
• Eduardo Peris

Beilstein J. Org. Chem. 2015, 11, 2584–2590, doi:10.3762/bjoc.11.278

• which the reported TEP was 2045 cm−1, therefore suggesting that the tris-MIC ligand B is a stronger electron donor than ligand A. However, this comparison must be taken with care, because the tris-carbene ligands A and B, not only differ in the nature of their carbenes (MIC vs NHC), but also in their

• -Ir(I) complex. Both techniques indicate that the ligand is a stronger electron donor than its related tris-NHC analogue. It is even more important to mention that the tris-MIC ligand is a stronger electron donor than its more closely related mono-MIC ligand – a situation that is also true for the

Biocatalysis for the application of CO₂ as a chemical feedstock

• Apostolos Alissandratos and
• Christopher J. Easton

Beilstein J. Org. Chem. 2015, 11, 2370–2387, doi:10.3762/bjoc.11.259

• -potential electron donor ferredoxin [26], with a requirement for strict anaerobicity, thus limiting the distribution of the reductive TCA cycle. As detailed in Scheme 2, the reductive TCA cycle contains three CO2 fixation steps [24]. Succinyl-CoA (5) is carboxylated by ferredoxin-dependent 2-oxoglutarate

• utilise H2 as an electron donor for the reduction of CO2 [118]. Furthermore, there is a growing list of examples of non-acetogenic metallo-FDHs, naturally catalysing formate oxidation, found to also be capable of catalysing CO2 reduction in vitro. FDH from Pseudomonas oxalaticus was the first isolated

• the visible spectrum (>1.35 eV) and coupled to FDH activity through a mediator to drive CO2 reduction. Two W-dependent FDHs, isolated from the syntrophic bacterium Syntrophobacter fumaroxidans, showed high catalytic activity for CO2 reduction, using reduced methyl viologen as the electron donor. Later

Photoinduced 1,2,3,4-tetrahydropyridine ring conversions

• Baiba Turovska,
• Henning Lund,
• Viesturs Lūsis,
• Anna Lielpētere,
• Edvards Liepiņš,
• Sergejs Beljakovs,
• Inguna Goba and
• Jānis Stradiņš

Beilstein J. Org. Chem. 2015, 11, 2166–2170, doi:10.3762/bjoc.11.234

• corresponding ground state species. The reaction between photochemically generated radical cations and radical anions by electron transfer from photoexcited electron donor to electron acceptors is often reversible [37] thus reproducing the reactant pair without the formation of a chemical bond. As the dioxygen

Conformational equilibrium in supramolecular chemistry: Dibutyltriuret case

• Karina Mroczyńska,
• Małgorzata Kaczorowska,
• Erkki Kolehmainen,
• Ireneusz Grubecki,
• Marek Pietrzak and
• Borys Ośmiałowski

Beilstein J. Org. Chem. 2015, 11, 2105–2116, doi:10.3762/bjoc.11.227

• complexes The VT 1H NMR experiments were conducted to have a deeper insight into the nature of the rotameric equilibrium within the complexes. The following salts were chosen (at various [1]:[benzoate] ratios [1] = 18.9 mmol dm−3): a) unsubstituted 5 (R = H), b) carrying electron donor 2 (R = NMe2) and c

Profluorescent substrates for the screening of olefin metathesis catalysts

• Raphael Reuter and
• Thomas R. Ward

Beilstein J. Org. Chem. 2015, 11, 1886–1892, doi:10.3762/bjoc.11.203

• (umbelliferone) (9) upon ring-closing metathesis. The synthesis of coumarin derivatives using this approach was described in previous publications [20][21]. By introducing an electron donor in the 7-position, a fluorescent product is obtained upon ring-closing metathesis [22]. Synthesis of the profluorescent

Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics

• Alexander L. Kanibolotsky,
• Neil J. Findlay and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1749–1766, doi:10.3762/bjoc.11.191

• ) electron donor and polythiophene (PT) conjugated systems are highly popular classes of organic compounds which have shown fascinating conducting and electronic properties. The advantages of PT-based materials are their synthetic versatility, excellent film-forming properties and potential to increase the

• dithienyl-thieno-TTF unit and the localised nature of the LUMO led to donor–acceptor interactions in the solid phase, making it impossible for efficient overlap between LUMOs, which would normally be required for an efficient n-type semiconductor. BHJSCs were fabricated from 48 as the electron donor and

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• based on the conjugation of an acylated sylibin derivative (19) with L-ascorbic acid (20), tyrosol (21) and trolox alcohol (22) (Scheme 4) [44]. These compounds proved to have excellent electron donor, antiradical, antioxidant as well as cytoprotective abilities. Moreover, in a different research area

Preparative semiconductor photoredox catalysis: An emerging theme in organic synthesis

• David W. Manley and
• John C. Walton

Beilstein J. Org. Chem. 2015, 11, 1570–1582, doi:10.3762/bjoc.11.173

• where the electron can reduce an electron acceptor with a suitable redox potential to a radical anion (A–•) and/or the hole can oxidize an electron donor to the radical cation (D+•, Figure 1). Recombination, whereby the electron drops back down to the VB, occurs in competition with this in the bulk of

• a reaction partner because on photoactivation it supplies electrons and holes while also donating protons from surface hydroxy groups. An interesting adjunct to these results was our finding that aryloxy-, arylthio- and anilino-acetic acids, carrying electron donor substituents (2-, 3- or 4-MeO, t

• transformations an excess of a sacrificial electron donor (reductive quencher) is needed to scavenge the VB holes and prevent e−/h+ recombination. Alcohols and amines have been successfully deployed in this role. Reductions of nitroaromatics took place effectively in photoactivated aqueous TiO2 slurries, with

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

• chiral salt α’-[(S,S)-2]ClO4 without H2O, but has a similar donor arrangement. According to the molecular design by introduction of hydroxy groups and a ClO4− anion, many intermediate-strength intermolecular hydrogen bonds (2.6–3.0 Å) were observed in these crystals between electron donor molecules

• ][17], ethylenedioxy [18], and pyrazino [19]), due to the difficulty of chiral-crystal growth. In order to improve the crystallinity, the inclusion of hydroxy groups in the BEDT-TTF molecule has been postulated to produce hydrogen bonding interactions between electron-donor molecules, electron-acceptor

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• tetrafluoroborates showing that both electron-donor and electron-acceptor substituted phenyldiazonium tetrafluoroborates undergo efficient borylation with an equimolar amount of B2pin2 (Scheme 1); however, ortho-substituted phenyldiazonium salts were found to be either not efficient substrates (3f) or completely

• , iodination with I2 shows a higher sensitivity to electronic properties of substituents on the aromatic ring. Electron-acceptor substituted aryldiazonium compounds are excellent substrates while those with electron-donor groups react much less efficiently. The substitution of pyridine with collidine (2,4,6

• electron-donor or acceptor groups while ortho-substituted substrates are less reactive. A mechanism involving aryl radicals is suggested. The Suzuki–Miyaura reaction of SF5-phenylboronates with aryl iodides provided the cross-coupling biaryl products. In analogy to the borylation reaction, iodination of

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

• for various applications. They have been, for example, used as electron donor molecules to prepare electrically (super)conducting crystalline materials [4][5][6][7], as solar energy systems [8][9] or even as donor moieties in nonlinear optical (NLO) materials [10][11]. In the last decades one of the

Advances in the synthesis of functionalised pyrrolotetrathiafulvalenes

• Luke J. O’Driscoll,
• Sissel S. Andersen,
• Marta V. Solano,
• Dan Bendixen,
• Morten Jensen,
• Troels Duedal,
• Jess Lycoops,
• Cornelia van der Pol,
• Rebecca E. Sørensen,
• Karina R. Larsen,
• Kenneth Myntman,
• Christian Henriksen,
• Stinne W. Hansen and
• Jan O. Jeppesen

Beilstein J. Org. Chem. 2015, 11, 1112–1122, doi:10.3762/bjoc.11.125

• Southern Denmark, Campusvej 55, DK-5230, Odense M, Denmark 10.3762/bjoc.11.125 Abstract The electron-donor and unique redox properties of the tetrathiafulvalene (TTF, 1) moiety have led to diverse applications in many areas of chemistry. Monopyrrolotetrathiafulvalenes (MPTTFs, 4) and

• molecular machines [1][2][3][4][5], molecular and organic electronics [5][6][7], chemosensors [1][8][9][10][11], coordination chemistry [12][13][14], catalysis [15] and beyond [16][17][18][19][20][21]. This owes much to the strong electron-donor character of the TTF moiety and its derivatives, which have

• thermodynamically stable. These properties are responsible for the strong electron-donor character of TTF and its derivatives. Furthermore, the precise oxidation potential of a TTF derivative can be changed by the addition of electron-donating or electron-withdrawing substituents [4]. Usually, each of the three

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

• viologen [5][6], aniline [7][8], thiophene [9], anthraquinone [10] and ferrocene [11] have been previously studied. However, a particularly suitable redox-active molecule for molecular electronics is the well-known electron donor tetrathiafulvalene (TTF) molecule. Pristine TTF, as well as the

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

• (EPFL), Station 6, CH-1050 Lausanne, Switzerland 10.3762/bjoc.11.118 Abstract Two new photosensitizers featured with a cyanoacrylic acid electron acceptor (A) and a hybrid electron donor (D) of cyclopentadithiophene and dithiafulvenyl, either directly linked or separated by a phenyl ring, were

• ][8] have been used in the construction of photosensitizers. Not surprisingly, tetrathiafulvalene (TTF), as a strong π-electron donor, has been incorporated into different D–π–A systems for numerous potential applications [9][10][11][12][13][14]. However, TTF-sensitized solar cells have rarely been

• ) configured with DTF-substituted 4,4-dihexyl-4H-cyclopenta[2,1-b:3,4-b’]dithiophene (CPDT) as an electron-donor and cyanoacrylic acid as an electron-acceptor moiety. The incorporation of the rigid and coplanar electron-donating moiety CPDT to the DTF core could increase the electron-donating ability of the

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

• Sandrina Oliveira Dulce Belo Isabel C. Santos Sandra Rabaca Manuel Almeida C²TN, Instituto Superior Técnico, Universidade de Lisboa, Estrada Nacional 10, P-2695-066 Bobadela LRS, Portugal 10.3762/bjoc.11.106 Abstract A dissymmetric TTF-type electron donor, cyanobenzene-ethylenedithio

• formation of insoluble dcdb-TTF. The CNB-EDT-TTF 3 electron donor is thermally stable, not sensitive to oxygen and soluble in common solvents such as CH2Cl2, CHCl3 and AcOEt. The molecular structure and purity of the isolated compound after column chromatography were confirmed by 1H and 13C NMR spectroscopy

• [CNB-EDT-TTF]0/[CNB-EDT-TTF]+ and [CNB-EDT-TTF]+/[CNB-EDT-TTF]2+, respectively. Comparing the redox potentials of the new TTF electron donor 3 with the well-known BEDT-TTF donor also measured by us in the same conditions, as shown in Table 1, we can conclude that, as expected, the cyanobenzene group

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

• , respectively. These electrochemical studies show that α-tbtdt and α-mtdt are easier to oxidise than the related unsubstituted extended TTFs, with higher electron donor ability compared to related TTF-type donors with the exception of BET-TTF. Crystal structures Ketone I Compound I crystallises in the

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

• Gebze-Kocaeli, Turkey 10.3762/bjoc.11.46 Abstract This review aims to give an overview of the current status of our research on the synthesis of π-electron donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF, ET) analogues prepared from 1,8-diketones via a ring forming reaction. The new synthesized π

• molecule [28][40]. The most notable superconductivity was observed with the radical cation salts derived from the electron-donor molecule bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) as a (BEDT-TTF)2Cu[N(CN)2]Br salt at 12.5 K (resistive onset) [24]. The tetrathiafulvalene (TTF) ring system is one of

Synthesis of dinucleoside acylphosphonites by phosphonodiamidite chemistry and investigation of phosphorus epimerization

• William H. Hersh

Beilstein J. Org. Chem. 2015, 11, 184–191, doi:10.3762/bjoc.11.19

• has not been found [48][49][50]. Once purified, 7 exhibited a strong carbonyl peak in the infrared spectrum at 1654 cm−1, a surprisingly low frequency considering the downfield 13C chemical shift. This inconsistency is perhaps due to an effect caused by the electron-donor diisopropylamide groups. A

Come-back of phenanthridine and phenanthridinium derivatives in the 21st century

• Lidija-Marija Tumir,
• Marijana Radić Stojković and
• Ivo Piantanida

Beilstein J. Org. Chem. 2014, 10, 2930–2954, doi:10.3762/bjoc.10.312

• -phenylphenanthridines. Thus, the electron-donor properties of the exocyclic amines, especially at 8-position have a stronger influence on the electron density of aromatic atoms than the electron withdrawing effects of endocyclic iminium. Fine tuning of electron properties of EB can be easily achieved via chemical

• modulation of its amino groups at 3 and 8 positions of the phenanthridine ring [52][53]. Systematic changing of the ethidium bromide exocyclic amines into guanidine, pyrrole, urea, and various substituted ureas revealed importance of electron-donor properties of substituents at the 3- and 8-position of the

• phenanthridinium relative to the unmodified primary amino groups. Namely, derivatives of EB having substituents with weaker electron-donor properties exhibited a stronger fluorescence emission than EB, while a stronger electron-donating substituent exhibited a much lower fluorescence emission. Such behaviour could

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

• Diego Cortizo-Lacalle,
• Calvyn T. Howells,
• Upendra K. Pandey,
• Joseph Cameron,
• Neil J. Findlay,
• Anto Regis Inigo,
• Tell Tuttle,
• Peter J. Skabara and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2683–2695, doi:10.3762/bjoc.10.283

• interpenetrating network they form within a bulk heterojunction (BHJ), has led to intense research directed towards the synthesis of conjugated polymers for bulk heterojunction organic photovoltaics (OPVs) [1][2][3]. In these devices, the conjugated polymer acts as an electron donor and a soluble fullerene, most

An integrated photocatalytic/enzymatic system for the reduction of CO₂ to methanol in bioglycerol–water

• Michele Aresta,
• Angela Dibenedetto,
• Tomasz Baran,
• Antonella Angelini,
• Przemysław Łabuz and
• Wojciech Macyk

Beilstein J. Org. Chem. 2014, 10, 2556–2565, doi:10.3762/bjoc.10.267

• was evidenced by measuring the amount of photogenerated 1,4-NADH using water or water/glycerol as electron donor. Figure 3b illustrates the results of the photocatalytic regeneration of NADH in presence of various materials after 6 hours of irradiation. Interestingly, for [CrF5(H2O)]2−@TiO2 the yield

• NADH photoregeneration process when compared to the [CrF5(H2O)]2−@TiO2 photocatalyst. As mentioned above, glycerol was considered as an electron donor in aqueous solution. When only water was used in the photoreduction, the reaction rate was very low due to the weak ability of H2O to transfer electrons

• . Figure 10 shows the influence of the nature of the electron donor and the concentration of the electron mediator, on the reduction rate. The NADH regeneration rate exhibits a strong dependence on the concentration of glycerol, which plays the crucial role of a sacrificial electron donor. Figure 10 also