Cyclodextrin-based rotaxanes for polymer materials: challenge on simultaneous realization of inexpensive production and defined structures

• Yosuke Akae

Beilstein J. Org. Chem. 2024, 20, 3026–3049, doi:10.3762/bjoc.20.252

• tetrathiafulvalene (TTF) and a triazole ring (Figure 7A) [61]. CD was located around the TTF moiety under neutral conditions; however, it moved to the triazole ring, following TTF oxidization. Meanwhile, the structural control by exploring the solvent polarity was reported by Harada and co-workers using the α-CD

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

• tetrathiafulvalene (TTF) arms, adopting a 1,3-alternate conformation by default with two cavities for binding electron-poor guests between the TTFs (Figure 18). The authors demonstrated complexation with 1,3,5-trinitrobenzene and other electron-poor guests such as TCNQ. The N–H protons of the pyrrole subunits can

• electronic or geometrical properties upon oxidation or reduction. TTF and derivatives tweezers One of the most widely used electroactive moieties is tetrathiafulvalene (TTF). Its electron-donor π-system can form non-covalent interactions with various electron-poor π-systems, and those interactions can be

Photochromic derivatives of indigo: historical overview of development, challenges and applications

• Gökhan Kaplan,
• Zeynel Seferoğlu and
• Daria V. Berdnikova

Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23

• incorporating redox-active tetrathiafulvalene (TTF) residues (Figure 7), known for their ability to form intramolecular π-dimers upon two-electron oxidation [47]. Thus, upon irradiation of the oxidized molecule 24 with 660 nm light, the thermal half-life of the Z-isomer exhibited a significant increase

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

• Christina Schøttler,
• Kasper Lund-Rasmussen,
• Line Broløs,
• Philip Vinterberg,
• Ema Bazikova,
• Viktor B. R. Pedersen and
• Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2024, 20, 59–73, doi:10.3762/bjoc.20.8

• Tetrathiafulvalene (TTF, Figure 1) is a redox-active molecule that has been widely explored in materials chemistry and supramolecular chemistry [1][2][3][4][5][6][7][8]. TTF reversibly undergoes two sequential one-electron oxidations, generating first a radical cation (TTF+•) and subsequently a dication (TTF2

Introducing a new 7-ring fused diindenone-dithieno[3,2-b:2',3'-d]thiophene unit as a promising component for organic semiconductor materials

• Valentin H. K. Fell,
• Joseph Cameron,
• Alexander L. Kanibolotsky,
• Eman J. Hussien and
• Peter J. Skabara

Beilstein J. Org. Chem. 2022, 18, 944–955, doi:10.3762/bjoc.18.94

• , compound 6 features a quinoidal antiaromatic [10] structure. Antiaromaticity is reported to further decrease the energy gap. The electron-rich dithiole units provide an extended tetrathiafulvalene structure, leading to compound 7 exhibiting two reversible one-electron oxidations [25]. Fused thiophenes have

Annulation of a 1,3-dithiole ring to a sterically hindered o-quinone core. Novel ditopic redox-active ligands

• Sergey V. Norkov,
• Anton V. Cherkasov,
• Andrey S. Shavyrin,
• Maxim V. Arsenyev,
• Viacheslav A. Kuropatov and
• Vladimir K. Cherkasov

Beilstein J. Org. Chem. 2021, 17, 273–282, doi:10.3762/bjoc.17.26

• -quinone-tetrathiafulvalene-o-quinone and o-quinone-(p-phenylene extended tetrathiafulvalene)-o-quinone were found to display switching SMM [4][5][6][7] or unique luminescent properties [8]. There are many reports describing the preparation of p-quinone derivatives annulated with a 1,3-dithiole moiety [9

• -chloro-o-quinone (1) with alkali metal salts of dithiocarboxylic acids. In fact, this procedure is suitable for the synthesis of such annulated o-quinone derivatives including di-o-quinones bridged by tetrathiafulvalene or p-phenylene-extended tetrathiafulvalene spacers 3a–c (Scheme 1, route 1) [14][15

Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

• Henrik Hupatz,
• Marius Gaedke,
• Hendrik V. Schröder,
• Julia Beerhues,
• Arto Valkonen,
• Fabian Klautzsch,
• Sebastian Müller,
• Felix Witte,
• Kari Rissanen,
• Biprajit Sarkar and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2020, 16, 2576–2588, doi:10.3762/bjoc.16.209

• synthetic molecular machines. Developing switchable and specifically designed crown ethers enables the implementation of function into molecular assemblies. Seven tailor-made redox-active crown ethers incorporating tetrathiafulvalene (TTF) or naphthalene diimide (NDI) as redox-switchable building blocks are

• electrochemical output. For example, crown ethers containing tetrathiafulvalene (TTF) derivatives, which enable two reversible oxidation processes from the neutral to the dicationic state, were applied to sense various cations, e.g., alkali metal ions, Pb2+, and Ba2+ [18][19][20][21]. Furthermore, with the first

Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes

• Aya Yoshimura,
• Hitoshi Kimura,
• Kohei Kagawa,
• Mayuka Yoshioka,
• Toshiki Itou,
• Dhananjayan Vasu,
• Takashi Shirahata,
• Hideki Yorimitsu and
• Yohji Misaki

Beilstein J. Org. Chem. 2020, 16, 974–981, doi:10.3762/bjoc.16.86

• systems; electrochemical properties; extended π-conjugation; digital simulation analysis; tetrathiafulvalene; Introduction Tetrathiafulvalenes (TTFs) with extended π-conjugation have attracted attention as possible components of functional materials, such as molecular conductors, field-effect transistors

• ), such as 4 (Figure 1), and the electrochemical properties of these representatives should be brought to light. Herein, we report the synthesis and electrochemical properties of tetrathiafulvalene derivatives 1–4. Results and Discussion Synthesis First, we tried to synthesize compounds 1 and 2 in one

Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

• ; supramolecular chemistry; tetrathiafulvalene; Introduction Undoubtedly, the exploration of nature’s molecular machines in the last century led to a paradigm change of how we think about working and organization processes on the molecular level [1][2][3]. Inspired by the way how energy and concentration

• “clean” stimulus is often preferred. One of the most frequently used and thoroughly characterized “clean” switches to control molecular motion of MIMs is tetrathiafulvalene (TTF, 1) and its derivatives (Figure 1). TTF is a redox-switchable organosulfur compound, which exhibits ideal properties for the

• introduction to readers new to the field of TTF-switchable MIMs. Review 1. Tetrathiafulvalene – an (almost) perfect molecular switch Whereas inorganic chemists are used to commonly handle metal-based compounds in different oxidation states, only a small selection of organic molecules [22] can be reversibly

Structure–property relationships and third-order nonlinearities in diketopyrrolopyrrole based D–π–A–π–D molecules

• Jan Podlesný,
• Lenka Dokládalová,
• Oldřich Pytela,
• Adam Urbanec,
• Milan Klikar,
• Numan Almonasy,
• Tomáš Mikysek,
• Jaroslav Jedryka,
• Iwan V. Kityk and
• Filip Bureš

Beilstein J. Org. Chem. 2017, 13, 2374–2384, doi:10.3762/bjoc.13.235

• -N,N’-dimethylaniline tetrathiafulvalene derivatives showed third-order nonlinear optical susceptibilities within a range of 20–32 pm2/V2 [40], whereas quinoline push-pull derivatives embedded in polymethylmethacrylate matrix possess a THG susceptibility equal to 46 pm2/V2 [41]. Reference inorganic

Protonated paramagnetic redox forms of di-o-quinone bridged with p-phenylene-extended TTF: A EPR spectroscopy study

• Nikolay O. Chalkov,
• Vladimir K. Cherkasov,
• Gleb A. Abakumov,
• Andrey G. Starikov and
• Viacheslav A. Kuropatov

Beilstein J. Org. Chem. 2016, 12, 2450–2456, doi:10.3762/bjoc.12.238

• -extended tetrathiafulvalene connector provides a quite effective electronic communication channel between dioxolene coordination sites. It was found that the deprotonated, direduced o-quinone-exTTF-o-quinone is capable to reduction of the metal copper in solution. The radical anion species formed in this

• ; EPR spectroscopy; extended tetrathiafulvalene; protonated semiquinone; Introduction The main idea that led to the creation of the system constructed of two o-quinone terminal moieties bridged with annulated extended tetrathiafulvalene (TTF) insertion, was an attempt to explore acceptor–donor–acceptor

Urethane tetrathiafulvalene derivatives: synthesis, self-assembly and electrochemical properties

• Xiang Sun,
• Guoqiao Lai,
• Zhifang Li,
• Yuwen Ma,
• Xiao Yuan,
• Yongjia Shen and
• Chengyun Wang

Beilstein J. Org. Chem. 2015, 11, 2343–2349, doi:10.3762/bjoc.11.255

• Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310012, China 10.3762/bjoc.11.255 Abstract This paper reports the self-assembly of two new tetrathiafulvalene (TTF) derivatives that contain one or two urethane groups. The formation of nanoribbons was evidenced by scanning electron

• driving forces for self-assembly of TTF derivatives were mainly hydrogen bond interactions and π–π stacking interactions. The electronic conductivity of the T1 and T2 films was tested by a four-probe method. Keywords: hydrogen bond; nanoribbon; self-assembly; tetrathiafulvalene; urethane; Introduction

• intermolecular interactions in molecular self-assembly systems. Therefore, molecules containing urea, amide and other similar groups have been investigated because these molecules can easily generate intermolecular hydrogen bonds [7][8][9]. Tetrathiafulvalene (TTF) derivatives have been widely investigated in

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

• sulfur-containing molecules and since the early 1990s, tetrathiafulvalene (TTF) supramolecular chemistry. Before I went to Odense, the group had developed a very useful method of in situ generation of TTF thiolate anion from cyanoethylated precursors, which greatly simplifies the modification of the TTF

[2.2]Paracyclophane derivatives containing tetrathiafulvalene moieties

• Laura G. Sarbu,
• Lucian G. Bahrin,
• Peter G. Jones,
• Lucian M. Birsa and
• Henning Hopf

Beilstein J. Org. Chem. 2015, 11, 1917–1921, doi:10.3762/bjoc.11.207

• of Inorganic and Analytical Chemistry, Technical University of Braunschweig, Hagenring 30, D-38106 Braunschweig 10.3762/bjoc.11.207 Abstract The synthesis of [2.2]paracyclophane derivatives containing tetrathiafulvalene units has been accomplished by the coupling reaction of 4-([2.2]paracyclophan-4

• -dithiolium salts; [2.2]paracyclophane; regioselective bromination; stereoisomers; tetrathiafulvalenes; Introduction Tetrathiafulvalene (TTF) and its derivatives have been extensively studied with respect to their applications as organic metals and superconductors [1][2]. These properties are a consequence

• of the π-donor properties of TTF and of its important intermolecular interactions in the solid state through extended π-orbitals. The design of new tetrathiafulvalene derivatives has targeted those systems where the intermolecular interactions between planar molecules are more effective and the solid

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

• Abstract The aim of this review is to give an update on current progress in the synthesis, properties and applications of thiophene-based conjugated systems bearing tetrathiafulvalene (TTF) units. We focus mostly on the synthesis of poly- and oligothiophenes with TTF moieties fused to the thiophene units

• in organic field effect transistors and solar cells. Keywords: donor; oligothiophene; organic electronics; polythiophene; semiconductor; tetrathiafulvalene; Introduction Sulfur-rich π-functional systems are important building blocks in materials chemistry. Among them, tetrathiafulvalene (TTF

• the preparation of TTF mixed valance state materials, which showed superconducting properties [25]. Fusing the TTF unit with dithiin rings in bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) led to the extension of 1D π–π stacking intermolecular interactions in a donor sheet of a mixed valance state

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

• Masahiko Iyoda and
• Masashi Hasegawa

Beilstein J. Org. Chem. 2015, 11, 1596–1613, doi:10.3762/bjoc.11.175

• 10.3762/bjoc.11.175 Abstract The construction of redox-active supramolecular assemblies based on star-shaped and radially expanded tetrathiafulvalene (TTF) oligomers with divergent and extended conjugation is summarized. Star-shaped TTF oligomers easily self-aggregate with a nanophase separation to

• nanostructured fibers and rods by controlling the supramolecular assembly, oxidation states, and counter anions employed. Keywords: conducting fibers; star-shaped molecules; supramolecular assembly; tetrathiafulvalene oligomers; Introduction Tetrathiafulvalene (TTF) chemistry first attracted enthusiastic

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 crystals. Racemic and enantiopure bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) derivatives possessing hydroxymethyl groups as the source of hydrogen bonds were designed. The novel racemic trans-vic-(hydroxymethyl)(methyl)-BEDT-TTF 1, and racemic and enantiopure trans-vic-bis(hydroxymethyl

• resistance of the chiral carbon nanotubes in a magnetic field were observed between enantiomers [4][5][6]. One method of constructing chiral crystals is through the use of chiral molecules as building blocks. Tetrathiafulvalene derivatives such as TTF (3) and BEDT-TTF (4) have been investigated considerably

• due to their ability to form radical cation salts with interesting conductive and magnetic properties (Figure 1). The influence of chirality in the TTF molecules on the crystal structure and physical properties has been shown by Avarvari’s (R)-, (S)- and racemic (±)-(ethylenedithio(tetrathiafulvalene

Tetrathiafulvalene chemistry

• Peter J. Skabara and
• Marc Sallé

Beilstein J. Org. Chem. 2015, 11, 1528–1529, doi:10.3762/bjoc.11.167

• Peter J. Skabara Marc Salle WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, United Kingdom MOLTECH-Anjou, Université d’Angers, UMR CNRS 6200, 2 Bd Lavoisier, 49045 Angers Cedex, France 10.3762/bjoc.11.167 Keywords: tetrathiafulvalene; TTF

• ; Tetrathiafulvalene (TTF) is a fascinating system: it is quite rare to find a synthetic molecule endowed with such a simple architecture that is capable of concentrating intense interest from various communities of chemists! This modest-sized molecule which consists of only 14 atoms, was synthesized in the early

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

• , Université de Sfax, Route de Soukra; Km 4; BP: 802, 3038, Sfax, Tunisia MEM, High School of Technology (ESTM), University, Moulay Ismail, Meknès, Morocco 10.3762/bjoc.11.149 Abstract The synthesis and full characterization of two tetrathiafulvalene-appended azine ligands, namely 2-([2,2’-bi(1,3

• ; tetrathiafulvalene; X-ray; Introduction Tetrathiafulvalene (TTF) is known to have excellent electron-donating properties resulting in stable radical cation (TTF•+) and dication (TTF2+) species from two sequential and reversible oxidation processes. The huge interest in the synthesis of TTF and its very numerous

• (1,3-dithiolylidene)]-4-yl)picolinaldehyde (1): This compound was prepared as previously described [38]. Stannylated tetrathiafulvalene (0.50 g, 1.36 mmol) and 6-bromo-2-pyridinecarboxaldehyde (0.34 g, 1.36 mmol) were dissolved in toluene (20 mL) and [Pd(PPh3)4] (0.156 g, 0.135 mmol) was added. The

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

• Physical-Organic Chemistry and Coal Chemistry, 02160 Kyiv, Ukraine 10.3762/bjoc.11.129 Abstract Two novel tetrathiafulvalene (TTF) containing compounds 1 and 2 have been synthesised via a four-fold Stille coupling between a tetrabromo-dithienoTTF 5 and stannylated thiophene 6 or thiazole 4. The optical

• interactions; organic field effect transistor (OFET); organic semiconductors; tetrathiafulvalene; thiazole; Introduction The TTF moiety has received much attention in the field of organic electronics owing to its reliable redox behaviour [1], good charge transport properties [2] and scope for

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

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

• to the N-arylation of MPTTFs and BPTTFs using a variety of aryl halides. Keywords: heterocycles; protecting groups; sulfur chemistry; tetrathiafulvalene; Ullman coupling; Introduction Tetrathiafulvalene (TTF) derivatives are of considerable interest in the fields of supramolecular chemistry and

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

• Flavia Pop Narcis Avarvari Université d'Angers, CNRS, Laboratoire MOLTECH-Anjou, UMR 6200, UFR Sciences, Bât. K, 2 Bd. Lavoisier, 49045 Angers, France 10.3762/bjoc.11.124 Abstract Enantiopure (R,R) and (S,S)-dimethyl-bis(ethylenedithio)tetrathiafulvalene monosulfones have been synthesized by the

• 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

• time in the middle of 80s by Dunitz and Wallis through the synthesis of the (S,S,S,S)-enantiomer of tetramethyl-bis(ethylenedithio)tetrathiafulvalene (TM-BEDT-TTF) (Scheme 1) [1], thus opening opportunities towards the preparation of chiral molecular conductors [2]. Since then a large number of chiral

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

• -molecule electrical transport properties of a molecular wire containing a π-extended tetrathiafulvalene (exTTF) group and its charge-transfer complex with F4TCNQ. We form single-molecule junctions using the in situ break junction technique using a homebuilt scanning tunneling microscope with a range of

• theoretical calculations. To the best of our knowledge, these are the first reported single-molecule conductance measurements on a molecular charge-transfer species. Keywords: break junction measurements; charge-transfer complex; DFT-based transport; molecular electronics; tetrathiafulvalene; Introduction

• 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

• unit. Keywords: donor–acceptor systems; dye-sensitized solar cells; electrochemistry; intramolecular charge transfer; Knoevenagel reaction; tetrathiafulvalene; Introduction Dye-sensitized solar cells (DSSCs) have been intensively investigated as an alternative to silicon-based solar cells [1][2][3][4

• ][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