A novel hexakis(tetrathiafulvalene) derivative: synthesis, structure and electrochemical properties

Christensen, Christian A.; Batsanov, Andrei S.; Becher, Jan

doi:10.1039/a909882h

Cited by 29 publications

(14 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Two recent and outstanding examples of multiple TTF containing molecules are the hexakis(TTF) derivative 58 and the TTF tetramer 59 . Compound 58 was prepared by the groups of Bryce and Becher in an efficient one‐pot synthesis in which a sixfold reaction occurs to open the way to the convergent construction of higher TTF oligomers and dendrimers 78. Compound 59 is the first example of a helical tetrathiafulvalene tetramer and was prepared by Iyoda et al79 Both compounds were synthesized by using cross‐ and homocoupling reactions of tetrathiafulvalenylzinc derivatives, and in their neutral state have a tight helical conformation with closely situated terminal TTF rings.…”

Section: Current Trends In the Development Of New Ttf‐containing Mmentioning

confidence: 99%

New Concepts in Tetrathiafulvalene Chemistry

Segura

Martı́n

2001

Angew. Chem. Int. Ed.

862

402

View full text Add to dashboard Cite

Tetrathiafulvalene (TTF) and its derivatives were originally prepared as strong electron‐donor molecules for the development of electrically conducting materials. This Review emphasizes how TTF and its derivatives offer new and in some cases little‐exploited possibilities at the molecular to the supramolecular levels, as well as in macromolecular aspects. TTF is a well‐established molecule whose interest goes beyond the field of materials chemistry to be considered an important building block in supramolecular chemistry, crystal engineering, and in systems able to operate as machines. At the molecular level, TTF is a readily available molecule which displays a strong electron‐donor ability. However, its use as a catalyst for radical–polar crossover reactions, thus mimicking samarium iodide chemistry, has only recently been addressed. Important goals have been achieved in the use of TTF at the macromolecular level where TTF‐containing oligomers, polymers, and dendrimers have allowed the preparation of new materials that integrate the unique properties of TTF with the processability and stability that macromolecules display. The TTF molecule has also been successfully used in the construction of redox‐active supramolecular systems. Thus, chemical sensors and redox‐switchable ligands have been prepared from TTF while molecular shuttles and molecular switches have been prepared from TTF‐containing rotaxanes and catenanes. A large synthetic effort has been devoted to the preparation of the so‐called organic ferromagnets, many of which are derived from TTF. The main task in these systems is the introduction of ferromagnetic coupling between the conduction electrons and localized electrons. TTF has also played a prominent role in molecular electronics where TTF‐containing D‐σ‐A molecules have allowed the preparation of the first confirmed unimolecular rectifier. Recently, it has been confirmed that TTF can display efficient nonlinear optic (NLO) responses in the second and third harmonic generation as well as a good thermal stability. These findings can be combined with the redox ability of TTF as an external stimuli to provide a promising strategy for the molecular engineering of switchable NLO materials. Fullerenes endowed with TTF exhibit outstanding photophysical properties leading to charge‐separated (CS) states that show remarkable lifetimes.

show abstract

Section: Current Trends In the Development Of New Ttf‐containing Mmentioning

confidence: 99%

New Concepts in Tetrathiafulvalene Chemistry

Segura

Martı́n

2001

Angew. Chem. Int. Ed.

862

402

View full text Add to dashboard Cite

show abstract

“…Analogues of 11 have been obtained recently using different methodologies. [17,18] Dynamic NMR Studies 1 H NMR studies on 4 showed that the molecule is not planar in solution. The difference in chemical shift for the two diastereotopic protons H a and H b observed at 20°C suggests that the molecule exists as the two conformers A and B (Figure 1) which interconvert slowly (by a boatϪboat flipping of the central ring) on the NMR timescale at this temperature giving a four-line AB system J AB ഠ 13 Hz).…”

Section: Scheme 1 Synthesis Of 4؊7mentioning

confidence: 99%

“…[5,21] Theoretical calculations have established that steric hindrance introduced by benzoannulation of the central quinodimethane unit determines the saddle-shape of the neutral molecules. [14] The strong electron donor ability of the title ring system has led to its use as a component of intermolecular [5,8,21] and intramolecular [11,17,18,22] chargetransfer systems.…”

Section: Introductionmentioning

confidence: 99%

Hydroxymethyl-Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-Dihydroanthracene π-Electron Donors as Synthetic Intermediates for Supramolecular Structures

et al. 2001

View full text Add to dashboard Cite

The synthesis of new derivatives of 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene is reported. 1 H NMR studies on compound 4 are consistent with two conformers of the saddle-shaped molecule which interconvert by a boat−boat flipping of the central ring at high temperature. The hydroxymethyl substituent of 4 is readily esterified to yield the benzoyl and 2-naphthaloyl ester derivatives 5a and 5b, respectively, and the dimer and the trimer structures 6 and 7, respectively, by reaction with benzoyl chloride, 2-naphthaloyl chloride, 1,4-benzenedicarbonyl chloride and 1,3,5-benzenetricarbonyl chloride. Deprotonation of 9-(4,5-dimethyl-1,3-dithiol-2-ylidene)-10-(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (8) using lithium bis(trimethylsilyl) amide (LHMDS) followed by in situ quenching of the lithiated intermediate with methylchloroformate gave the diester derivative 10 (96% yield), whereas using LDA gave the monoester

show abstract

“…Many of them, linked by a flexible chain, XðCHÞ n X (X¼ S; Se; n ¼ 1; 2, 3, y), were prepared by using two different multi-step strategies. The first one involves a cross-coupling reaction between two singlebridged dithiones or dithiolium salts (61,62) and the second is based on the useful chalcogenolate protectiondeprotection method developed by Becher and co-workers (63) and recently used to easily prepare a hexakis-(tetrathiafulvalene) exhibiting a relatively dense crystal packing structure (64). However, the main difficulty encountered remains the production of CTC and RIS as single crystals.…”

Section: Ttf With Extended P-conjugationmentioning

confidence: 99%

Dimensionality and Electrical Properties in Organic Synthetic Metals—Current Results through Selected Recent Examples

Fabre

2002

Journal of Solid State Chemistry

View full text Add to dashboard Cite

A novel hexakis(tetrathiafulvalene) derivative: synthesis, structure and electrochemical properties

Cited by 29 publications

References 17 publications

New Concepts in Tetrathiafulvalene Chemistry

New Concepts in Tetrathiafulvalene Chemistry

Hydroxymethyl-Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-Dihydroanthracene π-Electron Donors as Synthetic Intermediates for Supramolecular Structures

Dimensionality and Electrical Properties in Organic Synthetic Metals—Current Results through Selected Recent Examples

Contact Info

Product

Resources

About