3,6-Carbazole vs 2,7-carbazole: A comparative study of hole-transporting polymeric materials for inorganic–organic hybrid perovskite solar cells

• Wei Li,
• Munechika Otsuka,
• Takehito Kato,
• Yang Wang,
• Takehiko Mori and
• Tsuyoshi Michinobu

Beilstein J. Org. Chem. 2016, 12, 1401–1409, doi:10.3762/bjoc.12.134

• -EDOT were calculated according to Equation 1: where φFc/Fc+ is the redox potential of the ferrocene/ferrocenium (Fc/Fc+) couple measured under the same conditions (in this case, 0.09 V vs the Ag/Ag+electrode). 2,7-Cbz-EDOT has a deeper HOMO level than 3,6-Cbz-EDOT. This was also the case for the lowest

On the mechanism of imine elimination from Fischer tungsten carbene complexes

• Philipp Veit,
• Christoph Förster and
• Katja Heinze

Beilstein J. Org. Chem. 2016, 12, 1322–1333, doi:10.3762/bjoc.12.125

• dissociation, followed by an oxidative addition/pseudorotation/reductive elimination pathway with short-lived, elusive seven-coordinate hydrido tungsten(II) intermediates cis(N,H)-W(CO)4(H)(Z-15) and cis(C,H)-W(CO)4(H)(Z-15). Keywords: carbene complexes; ferrocene; imine; mechanism; tungsten; Introduction

• S27). In full accordance with the above observations, UV–vis spectra recorded during the thermal treatment of W(CO)5(E-2) in toluene (100 °C) show the clean decay of the characteristic bands of W(CO)5(E-2) at 360 and 391 nm. The ferrocene based absorption band around 500 nm remains essentially

• . Potentials are referenced against the decamethylferrocene/decamethylferrocenium couple (E½ = −525 ± 5 mV vs ferrocene/ferrocenium under our experimental conditions) and are given relative to the ferrocene/ferrocenium couple. UV–vis/NIR spectra were recorded on a Varian Cary 5000 spectrometer by using 1.0 cm

Synthesis, fluorescence properties and the promising cytotoxicity of pyrene–derived aminophosphonates

• Jarosław Lewkowski,
• Maria Rodriguez Moya,
• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Renata Kontek and
• Gabriela Gajek

Beilstein J. Org. Chem. 2016, 12, 1229–1235, doi:10.3762/bjoc.12.117

• [2] or anticancer properties [3]. Various C-aryl substituted derivatives of phosphonoglycine have been synthesized including those of benzene and several polycyclic aromatic hydrocarbons [4], five- [5] and six-membered [6] heteroaromatic compounds and even ferrocene [7]. In contrast, pyrene-based

Superstructures with cyclodextrins: chemistry and applications III

• Gerhard Wenz and
• Eric Monflier

Beilstein J. Org. Chem. 2016, 12, 937–938, doi:10.3762/bjoc.12.91

• the group of B. J. Ravoo using host–guest interactions between polyethyleneimine grafted with β-CD and a polyamidoamine dendrimer decorated with ferrocene. The formation of the superstructures was reversible by electrochemical oxidation of the ferrocene moieties [6]. Furthermore, significant progress

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

• various fractions of IC70BA is shown in Table 1. In order to analyze the electrochemical properties of the IC70BA fractions, cyclic voltammetry was performed on each fraction. The first reduction potentials of all 11 fractions were found to be in the range of −1.13 to −1.25 eV versus that of ferrocene

Copper-mediated arylation with arylboronic acids: Facile and modular synthesis of triarylmethanes

• H. Surya Prakash Rao and
• A. Veera Bhadra Rao

Beilstein J. Org. Chem. 2016, 12, 496–504, doi:10.3762/bjoc.12.49

• % yield (Table 3, entry 1). Similarly, the reaction of anthracen-9-yl(phenyl)methanol (9c) with phenylboronic acid (10a) provided the corresponding triarylmethane 11o in 82% yield (Table 3, entry 2). The last example in the genre is interesting, as one of the aryl rings is ferrocene in 11p. The reaction

• of ferrocene-1-yl(phenyl)methanol (9d) with phenyboronic acid (10a) was facile and it provided diphenylmethylferrocene (11p) without any difficulty in 71% yield. Modular synthesis of triarylmethanes The synthetic method that we developed, through which three different aromatic rings on the central

• respective pyrene-containing unsymmetrical triarylmethanes 11q–r in good yields (Table 3). Next, the coupling reaction of phenyl(ferrocenyl)methanol (9d) with thiophen-3-ylboronic acid (10m) provided triarylmethane 11s, which has ferrocene, thiophene and phenyl rings installed on the central carbon. The

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

• Jie Wang,
• Zhiqiang Qiu,
• Yiming Wang,
• Li Li,
• Xuhong Guo,
• Duc-Truc Pham,
• Stephen F. Lincoln and
• Robert K. Prud’homme

Beilstein J. Org. Chem. 2016, 12, 50–72, doi:10.3762/bjoc.12.7

• than are the dodecyl substituents of PAAddn. An interesting variation on the redox chemistry of ferrocene in polymer systems was presented by Zhu et al. who attached ferrocene, FC, as a substituent to branched poly(ethylene imine), BPEI, through reaction with ferrocenecarboxaldehyde to give the

• ferrocene substituted polymer, BPEI-FC [107]. Aqueous solutions of this polymer are about ten times more viscous than the precursor BPEI polymer as a consequence of the enhancement of polymer chain association because of the hydrophobicity of the ferrocene substituents of BPEI-FC. However, this viscosity is

• greatly deceased upon the addition of β-CD because host–guest complexation of ferrocene masks its hydrophobicity and the hydrophilic exterior of the complexing β-CD much decreases association between the polymer chains. The same effect occurs when hydrogen peroxide is added to aqueous BPEI-FC and the

Recent advances in metathesis-derived polymers containing transition metals in the side chain

• Ileana Dragutan,
• Valerian Dragutan,
• Bogdan C. Simionescu,
• Albert Demonceau and
• Helmut Fischer

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

• as prepared by controlled living ring-opening metathesis polymerization (ROMP) of the respective metal-incorporating monomers. Ferrocene- and other metallocene-modified polymers, macromolecules including metal-carbonyl complexes, polymers tethering early or late transition metal complexes, etc. are

• groups it became possible to synthesize a broad range of polymers and copolymers by ROMP [35][36]. On the other hand it is well-known that ferrocene and numerous transition metal sandwich complexes exhibit great redox stability that allows fine tuning of their properties and applications in

• electrochemistry, sensing, catalysis, nanomaterials, etc. [37][38][39][40]. Not surprisingly, therefore, attention of researchers has turned first on metallopolymers containing ferrocene [33][34][41][42][43]. Review Iron-containing polymers Following the first successful application of Mo–alkylidene catalysts by

Synthesis and photophysical characteristics of polyfluorene polyrotaxanes

• Aurica Farcas,
• Giulia Tregnago,
• Ana-Maria Resmerita,
• Pierre-Henri Aubert and
• Franco Cacialli

Beilstein J. Org. Chem. 2015, 11, 2677–2688, doi:10.3762/bjoc.11.288

• gap (ΔEg) using ferrocene (Fc) as reference [51]. The IP, EA energy levels and ΔEg were calculated according to Equations 1–3 [52][53]. where: −4.80 eV represents the position of the Fc+/Fc redox couple in the energetic diagram [51]; +0.44 V is the redox potential of Fc+/Fc vs Ag. As indicated in

Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors

• Thibault E. Schmid,
• Sammy Drissi-Amraoui,
• Christophe Crévisy,
• Olivier Baslé and
• Marc Mauduit

Beilstein J. Org. Chem. 2015, 11, 2418–2434, doi:10.3762/bjoc.11.263

• acceptors, which were the focus of a work reported by Feringa and co-workers in 2008 [28]. In this study, the efficiency of ferrocene-based ligands was investigated for the addition of Grignard reagents onto ethyl sorbate, using CuBr·SMe2 as the copper source. Reversed Josiphos L8 was selected as the most

• adducts [38]. Various ligands were tested and the best catalytic performance was achieved using bidentate ferrocene-based ligand L14 in combination with tetrakis(acetonitrile)copper(I) perchlorate as the copper source. The conversion of aromatic linear dienones 67 was reported with a complete

Size-controlled and redox-responsive supramolecular nanoparticles

• Raquel Mejia-Ariza,
• Gavin A. Kronig and
• Jurriaan Huskens

Beilstein J. Org. Chem. 2015, 11, 2388–2399, doi:10.3762/bjoc.11.260

• ) grafted with β-cyclodextrin (CD) and a positively charged ferrocene (Fc)-terminated poly(amidoamine) dendrimer, with a monovalent stabilizer at the surface. Fc was chosen for its loss of CD-binding properties when oxidizing it to the ferrocenium cation. The ionic strength was shown to play an important

• charged polymers and dendrimers. In order to use these SNPs for biomedical applications, in particular for drug delivery, a stimulus-responsive self-assembled system is desired for controlled cargo release. Ferrocene (Fc) is a ubiquitous redox-responsive molecule that is associated with a reversible one

• protein isolation method [24]. So far, this concept has not been applied to SNPs. Here, we aim to make SNPs with a redox-switchable assembly/disassembly mechanism. As a proof of concept, we used positively charged CD-grafted poly(ethylene imine) (CD-PEI) as a host, positively charged ferrocene-terminated

A new approach to ferrocene derived alkenes via copper-catalyzed olefination

• Vasily M. Muzalevskiy,
• Aleksei V. Shastin,
• Alexandra D. Demidovich,
• Namiq G. Shikhaliev,
• Abel M. Magerramov,
• Victor N. Khrustalev,
• Rustem D. Rakhimov,
• Sergey Z. Vatsadze and
• Valentine G. Nenajdenko

Beilstein J. Org. Chem. 2015, 11, 2072–2078, doi:10.3762/bjoc.11.223

• , 28 Vavilov Street, Moscow 119991, Russia 10.3762/bjoc.11.223 Abstract A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine

• of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps. Keywords: catalytic olefination; copper catalysis; cyclic voltammetry; ferrocene; Introduction The introduction of complex functional fragments into the specified

• place of the target molecule is of current interest in modern synthetic chemistry [1]. From this point of view, the development of ferrocene-based molecules as crucial fragments of new materials and novel pharmacological entities is of great importance. Indeed, since the discovery of ferrocene [2] and

Supramolecular chemistry: from aromatic foldamers to solution-phase supramolecular organic frameworks

• Zhan-Ting Li

Beilstein J. Org. Chem. 2015, 11, 2057–2071, doi:10.3762/bjoc.11.222

• (SIOC). In the spring of 1985, the second semester of the fourth year, I entered Professor Zhendong Chen’s lab to perform my dissertation research. I stayed in the lab for about three months and prepared several ferrocene-derived conjugated molecules to study the homologous linearity [1]. I later

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

• ) and BHJSCs. So far, various electroactive units have been anchored aside the polythiophene backbone, including ferrocene [8], porphyrin [9], 2-carboxyanthraquinone [10], 1,3-dithiole-2-ylidenefluorene [11][12], dithiinoquinoxaline [13][14] and fullerene C60 [15][16]. The incorporation of acceptor

SmI₂-mediated dimerization of indolylbutenones and synthesis of the myxobacterial natural product indiacen B

• Nils Marsch,
• Peter G. Jones and
• Thomas Lindel

Beilstein J. Org. Chem. 2015, 11, 1700–1706, doi:10.3762/bjoc.11.184

• of 1,1'-dicinnamoylferrocenes had also afforded cis-phenyl-disubstituted cyclopentanols, presumably as a consequence of parallel orientation of the enone systems by fixation of the carbonyl oxygens by Sm(III) and tethering by the ferrocene unit [26]. A possible reason for our findings could be the

Synthesis and spectroscopic properties of β-triazoloporphyrin–xanthone dyads

• Dileep Kumar Singh and
• Mahendra Nath

Beilstein J. Org. Chem. 2015, 11, 1434–1440, doi:10.3762/bjoc.11.155

• porphyrins with diverse functionalities such as quinolone [19], ferrocene [20], carbohydrate [21] and fullerene [22] through a copper(I)-catalyzed Huisgen–Sharpless–Meldal 1,3-dipolar cycloaddition reaction [23][24]. Some of these triazolo-bridged porphyrin dyads have shown an efficient intramolecular energy

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

• compounds which are discussed in detail in this review. Review Synthetic routes to cyclophanes Addition reactions Mannich reaction: In 2001, Erker and co-workers [84] have reported the synthesis of amino-substituted [3]ferrocenophane through an intramolecular Mannich reaction starting with the ferrocene

• accomplished in a one-pot reaction under Wolff–Kishner reaction conditions to generate 223 and 259, respectively (Scheme 41). Cycloaddition reactions [2 + 2] Cycloaddition: Roemer and Lentz [175] have reported the synthesis of fluorinated ferrocenophanes from 1,10-bis(trifluorovinyl)ferrocene and 1,4-(1,10

• -ferrocenediyl)-1,1,2,2,3,3,4-heptafluorobutane. The authors have reported a [2 + 2] cycloaddition reaction under thermal conditions. 1,10-Bis(trifluorovinyl)ferrocene (261) was synthesized starting with diiodoferrocene 260 by Negishi-type coupling. Compound 261 was subjected to a [2 + 2] cycloaddition sequence

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

• argon atmosphere and at a scan rate of 0.1 Vs−1. The electrochemical cell consisted of a glassy carbon working electrode, Ag/AgNO3 reference electrode and a Pt wire counter electrode. It is worth mentioning that ferrocene was not employed as the inner reference since its oxidation potential overlaps

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

• (dppf)(OTf)2 (M = Pd or Pt; dppf = 1,1’-bis(diphenylphosphino)ferrocene; OTf = trifluoromethanesulfonate) in nitromethane at 40 °C converged into a single symmetrical M4L2 discrete species (Scheme 1, Figure 1b) [39]. It is worth noting that the through space interaction between the phenyl rings of the

• bulky 1,1’-bis(diphenylphosphino) ferrocene (dppf) coligand and the pyridine moieties force the exTTF unit to increase significantly its curvature in comparison to ligand L1 (56° vs 86° respectively between the 1,3-dithiol-2-ylidene mean planes (Figure 1)). This leads to the formation of the compact

• on the Pd metal center. In particular, whereas a 1,1’-bis(diphenylphosphino)ferrocene co-ligand promotes a clipping of the ligand pyridyl units and leads to a strong curvature of the exTTF moiety integrated in a M4L2 coordination cage, the use of a smaller co-ligand leads to the formation of a larger

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

• [11][12] have shown how rotamers can indeed influence the electronic coupling in bis-ruthenium complexes separated by oligoynediyl spacers. In addition, an increased interaction between redox centres upon linking them together in cyclic structures was previously observed in ferrocene-dimers [13]. Here

• Supporting Information File 1, Figure S4) using cyclic voltammetry (with a platinum-wire working electrode in the presence of internal ferrocene potential marker). They are very close to 1a and 2a, respectively, as expected. Using 3b as a reference compound, it is seen that all the other compounds are

• rotating the two TTF units around the ethyne bridge of 2.5 kJ mol−1 (see Supporting Information File 1). The electronic interactions between two TTFs being spanned by alkynyl or poly-alkynyl bridges are quite poor in comparison to other redox groups. Ferrocene units are only marginally better than TTFs

3α,5α-Cyclocholestan-6β-yl ethers as donors of the cholesterol moiety for the electrochemical synthesis of cholesterol glycoconjugates

• Aneta M. Tomkiel,
• Adam Biedrzycki,
• Jolanta Płoszyńska,
• Dorota Naróg,
• Andrzej Sobkowiak and
• Jacek W. Morzycki

Beilstein J. Org. Chem. 2015, 11, 162–168, doi:10.3762/bjoc.11.16

• electrode was a Bioanalytical Systems platinum inlay (1 mm in diameter), the auxiliary electrode was a platinum mesh (contained in a glass tube with a medium porosity glass frit), and the reference electrode was Ag/0.1 M AgNO3 in acetonitrile. The potential of the electrode vs the ferrocene/ferricinium ion

Redox active dendronized polystyrenes equipped with peripheral triarylamines

• Toshiki Nokami,
• Naoki Musya,
• Tatsuya Morofuji,
• Keiji Takeda,
• Masahiro Takumi,
• Akihiro Shimizu and
• Jun-ichi Yoshida

Beilstein J. Org. Chem. 2014, 10, 3097–3103, doi:10.3762/bjoc.10.326

• polymers [2][3][4][5][6][7][8] as scaffolds serves as a useful method for synthesizing organic functional materials having nanosize three-dimensional structures. Although there are many examples of redox-active dendrimers, including those equipped with ferrocene [9][10], triarylamines [11][12][13][14], and

Inherently chiral calix[4]arenes via oxazoline directed ortholithiation: synthesis and probe of chiral space

• Simon A. Herbert,
• Laura J. van Laeren,
• Dominic C. Castell and
• Gareth E. Arnott

Beilstein J. Org. Chem. 2014, 10, 2751–2755, doi:10.3762/bjoc.10.291

• examined as ligands in the palladium-catalyzed Tsuji–Trost allylation reaction, returning results comparable to their planar chiral ferrocene counterparts pointing towards future application of these types of compounds. Keywords: calix[4]arene; inherently chiral; ortholithiation; oxazoline; Tsuji–Trost

• calixarenes 5–8, we noted their similarity to planar chiral thioether oxazoline ferrocene ligands (9 in Figure 1) already reported by Dai and co-workers [35]. We therefore initiated a pilot study with our inherently chiral calix[4]arenes, using the palladium-catalyzed Tsuji–Trost allylation reaction (Scheme 3

• co-workers with respect to their planar chiral ferrocene derivatives (e.g., 9). Although it is unclear to us why the rate should be enhanced, the fact that it does bodes well for calix[4]arenes being investigated as ligands. On a less positive note, ligands 7b and 8 were completely ineffective, with

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

• acetonitrile. In both cases, a Ag wire reference electrode and a Pt counter-electrode, in the presence of Bu4NPF6 (0.1 M), were used. All the values are quoted versus the redox potential of the ferrocene/ferrocenium couple. Normalised UV–vis absorption spectra of 9 (black), 10 (red) and DPP core (11, green) in

The effect of permodified cyclodextrins encapsulation on the photophysical properties of a polyfluorene with randomly distributed electron-donor and rotaxane electron-acceptor units

• Aurica Farcas,
• Ana-Maria Resmerita,
• Pierre-Henri Aubert,
• Flavian Farcas,
• Iuliana Stoica and
• Anton Airinei

Beilstein J. Org. Chem. 2014, 10, 2145–2156, doi:10.3762/bjoc.10.222

• electronic affinity (EA), and the electrochemical band gaps (ΔEg) by using ferrocene (Fc) as a reference [45][46]. It should be mentioned that the encapsulated 1a or 1b moieties and 2 randomly distributed into the 3 backbone leads to the synthesis of compounds with smaller optical and electrochemical gaps