Stable Macrocyclic and Tethered Donor−Acceptor Systems. Intramolecular Bipyridinium and Tetrathiafulvalene Assemblies

Simonsen, Klaus B.; Zong, Kyukwan; Rogers, Robin D.; Cava, Michael P.; Becher, Jan

doi:10.1021/jo961782a

Cited by 65 publications

(33 citation statements)

References 32 publications

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“…[34] Cava, Becher, and co-workers synthesized an interesting series of compounds, 21±23, in which TTF units were covalently tethered, or bridged, to bipyridinium acceptors, allowing the extent of CT to be investigated as a function of the structure of the bridging group(s). [38] The synthesis proceeded via alkylation (or dialkylation) of the bipyridyl system with the appropriately functionalized TTF derivatives. Systems 21±23 showed very broad ICT bands with l max values of 624, 673, and 640 nm, respectively.…”

Section: Pyridinium and Bipyridinium Acceptorsmentioning

confidence: 99%

“…In this case, subtle conformational effects in the macrocycles are no doubt important. The X-ray crystal structure of 22 [38] provides one of the first solid-state structures of a TTF±s±A molecule in which ICT has been established in solution. The X-ray analysis confirmed the trans substitution of the TTF, and revealed significant bending of the TTF framework, no doubt induced by the strained macrocyclic ring.…”

Section: Pyridinium and Bipyridinium Acceptorsmentioning

confidence: 99%

“…[39] (This contrasts with the near-planar, strain-free TTF in macrocycle 6 [26] discussed above.) Analysis of the bond lengths [40] in the crystal structure of 22 [38] suggest a neutral (or near-neutral)…”

Section: Pyridinium and Bipyridinium Acceptorsmentioning

confidence: 99%

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Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Bryce

1999

Adv. Mater.

334

144

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Although tetrathiafulvalene (TTF) and its derivatives have been extensively studied for more than 25 years as p-electron donors in intermolecular charge-transfer materials, the intriguing potential of TTF as a donor in an intramolecular sense has only recently been developed. Many versatile, functionalized TTF building blocks are now readily available, and this article will review a range of compounds in which TTF is covalently linked to an electron acceptor moiety by a variety of linking units, sometimes giving rise to an intramolecular charge-transfer (ICT) interaction, which is most frequently manifested in the optical and electrochemical properties. In this context, acceptor subunits include: tetracyano-p-quinodimethane, quinones, electrondeficient aryl groups, pyridinium and bipyridinium units, fullerenes, phthalocyanines, and mesomerically conjugated carbonyl, thiocarbonyl, ester, and related groups. This work paves the way for more systematic and detailed studies of TTF±spacer±A molecules (where A is an acceptor) in which there is increased control of the structural, electronic, optical, and magnetic properties arising from ICT interactions in the ground state, or in the excited state.

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Section: Pyridinium and Bipyridinium Acceptorsmentioning

confidence: 99%

Section: Pyridinium and Bipyridinium Acceptorsmentioning

confidence: 99%

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Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Bryce

1999

Adv. Mater.

334

144

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“…The angle between the mean planes N 4 formed by the above mentioned nitrogen atoms, coordinated to Cu(1) and Cu(2), respectively, is 57.14 (12) , which is very close to the expected idealized angle between C-N bonds in 1,3-diaminobenzene (60 ). Aromatic rings of two LH À residues are almost parallel (the angle between mean planes of these rings is 6.38 (15) ) and are located at the distance about 3.3 A from each other.…”

Section: Crystal Structuresmentioning

confidence: 99%

“…The angle between aromatic rings of bipy molecule is 32.36 (15) . The distance of Cu (1) (8) A, and the separation between Cu(1) and Cu (2) 0 through the bipy bridge is 11.0440 (8) A.…”

Section: 7mentioning

confidence: 99%

A new approach towards ferromagnetic conducting materials based on TTF-containing polynuclear complexes

et al. 2010

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International audienceFive complexes containing binuclear cation [Cu2(LH)2]2+ (LH2 = 1 : 2 Schiff base of 1,3-diaminobenzene and butanedione monoxime) were prepared and characterized. Metathesis of one perchlorate anion in [Cu2(LH)2(H2O)2](ClO4)2 (1) by anionic TTF-carboxylate (TTF-CO2−) leads to the complex [Cu2(LH)2(CH3OH)2](TTF-CO2)(ClO4)*H2O (2). Reactions of 1 with substituted pyridines bipy, dpe and TTF-CH = CH-py result in formation of the complexes {[Cu2(LH)2(bipy)](ClO4)2}n*2nH2O (3), [Cu2(LH)2(dpe)2](ClO4)2*2CH3OH (4) and [Cu2(LH)2(TTF-CH = CH-py)(H2O)](ClO4)2*1.5H2O (5), where bipy = 4,4′-bipyridine, dpe = trans-(4-pyridyl)-1,2-ethylene and TTF-CH = CH-py = 1-(2-tetrathiafulvalenyl)-2-(4-pyridyl)ethylene. Whereas complex 2 is built from discrete ionic particles (with rather long Cu-S contacts), compounds 1 and 3 contain 1D polymeric chains, in which structural units are bonded through Cu-O bonds or through bridging bipy molecule, respectively. Dinuclear complexes 4 and 5 are linked though π-stacking of dpe or TTF-CH = CH-py, respectively. All complexes are characterized by dominating ferromagnetic behavior with J values in the range from +9.92(8) cm−1 to +13.4(2) cm−1 for Hamiltonian H = -JS1S2. Magnetic properties of the compounds, containing stacks of aromatic molecules in crystal structures (4 and 5), correspond to ferromagnetic intradimer and antiferromagnetic intermolecular interactions (zJ′ = −0.158(3) and −0.290(2) cm−1, respectively). It was found that TTF-CH = CH-py ligand in [Cu2(LH)2(TTF-CH = CH-py)(H2O)]2+ could be electrochemically oxidized to cation-radical form in the solution

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Synthesis and Characterisation of Macrobicyclic Tetrathiafulvalene-Bridged Cage Molecules

Blanchard¹,

Svenstrup²,

Rault‐Berthelot

et al. 1998

Eur. J. Org. Chem.

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A series of new macrobicyclic tetrathiafulvalenophanes of type 1 and 2 with three tetrathiafulvalene bridges has been prepared under high‐dilution conditions using a stepwise selective protection‐deprotection of tetrathiafulvalenethiolates. All the macrobicyclic tetrathiafulvalenes, along with the intermediate compounds 5 and 6 and the unexpected tetrathiafulvalene pentamers 17, were studied by cyclic voltammetry. An electrochemical investigation using the Bard‐Anson equation and thin‐layer cyclic voltammetry has been carried out, allowing an estimate of the number of electrons involved in each redox process of these multi‐redox compounds. The X‐ray crystal structure showing the unusual crystal packing of 2a is also presented.

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Stable Macrocyclic and Tethered Donor−Acceptor Systems. Intramolecular Bipyridinium and Tetrathiafulvalene Assemblies

Cited by 65 publications

References 32 publications

Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

A new approach towards ferromagnetic conducting materials based on TTF-containing polynuclear complexes

Synthesis and Characterisation of Macrobicyclic Tetrathiafulvalene-Bridged Cage Molecules

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