An Experimental and Computational Study on Intramolecular Charge Transfer: A Tetrathiafulvalene‐Fused Dipyridophenazine Molecule

Jia, Chunyang; Liu, Shixia; Tanner, Christian; Leiggener, Claudia; Neels, Antonia; Sanguinet, Lionel; Levillain, Eric; Leutwyler, Samuel; Hauser, Andreas; Decurtins, Silvio

doi:10.1002/chem.200601561

Cited by 179 publications

(165 citation statements)

References 48 publications

(32 reference statements)

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“…The absorption spectrum in the visible region is clearly dominated by a broad and strong band centered at 495 nm. Based on the computational results from analogous D--A molecules, [13,14] this electronic excitation can unequivocally be characterized as an intramolecular charge-transfer transition (ICT). Essentially, it corresponds to a one-electron excitation from the HOMO localized on the TTF moiety to the LUMO localized on the BTD fragment, hence, an electronic transition which typically occurs within fused D--A molecules.…”

Section: Photophysical Properties Of Ttf-btd (1)mentioning

confidence: 99%

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A Compact Tetrathiafulvalene–Benzothiadiazole Dyad and Its Highly Symmetrical Charge‐Transfer Salt: Ordered Donor π‐Stacks Closely Bound to Their Acceptors

Geng

Pfattner

Campos

et al. 2014

Chemistry A European J

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A compact and planar donor-acceptor molecule 1 comprising tetrathiafulvalene (TTF) and benzothiadiazole (BTD) has been synthesised and experimentally characterised by structural, optical and electrochemical methods. Solution processed and thermally evaporated thin films of 1 have also been explored as active material in organic field-effect transistors (OFETs). For these devices, a hole field-effect mobility of FE = (1.3 ± 0.5) ×10-3 cm 2 /Vs and of FE = (2.7 ± 0.4) ×10 -3 cm 2 /Vs could be determined for the solution processed and thermally evaporated thin films, respectively. An intense intramolecular charge-transfer (ICT) transition around 495 nm dominates the optical absorption spectrum of the neutral dyad, which also shows a weak emission from its ICT state. The iodine induced oxidation of 1 leads to a partially oxidised crystalline charge-transfer (CT) salt {(1) 2 I 3 }, and eventually also to a fully oxidized compound {1I 3 } ½I 2 .Single crystals of the former CT compound, exhibiting a highly symmetrical crystal structure, reveal a fairly good room temperature electrical conductivity of the order of 2 S cm -1 . The one-dimensional spin system bears compactly bonded BTD acceptors (spatial localisation of LUMO) along its ridge.

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Section: Photophysical Properties Of Ttf-btd (1)mentioning

confidence: 99%

“…However, it is also noticeable that the annulation of an acceptor unit to the TTF skeleton leads per se to a systematic lengthening of the central C=C bond. [13,14] …”

Section: Photophysical Properties Of Ttf-btd (1)mentioning

confidence: 99%

A Compact Tetrathiafulvalene–Benzothiadiazole Dyad and Its Highly Symmetrical Charge‐Transfer Salt: Ordered Donor π‐Stacks Closely Bound to Their Acceptors

Geng

Pfattner

Campos

et al. 2014

Chemistry A European J

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“…1a, where 4',5'-bis-(propylthio)-substituted tetrathiafulvalene (TTF) is fused to two different dipyridophenazine units, namely dipyrido[3,2-a:2',3'-c]phenazine (dppz) [13] and dipyrido[2,3-a:3',2'-c]phenazine (dppz').…”

Section: Introductionmentioning

confidence: 99%

Dual Luminescence and Long-Lived Charge-Separated States in Donor-Acceptor Assemblies Based on Tetrathiafulvalene-Fused Ruthenium(II)-Polypyridine Complexes

Leiggener¹,

Dupont²,

Liu³

et al. 2007

Chimia

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: The creation of long-lived charge-separated states in donor − acceptor assemblies has been the goal of many studies aimed at mimicking the primary processes in photosynthesis. Here we present such assemblies based on tetrathiafulvalene (TTF) as electron donor and a dipyridophenazine (dppz) unit as electron acceptor in the form of a fused ligand (TTF-dppz) coordinated to ruthenium(II) via the dipyrido coordination site and with 2,2'-bipyridine (bpy) as auxiliary ligand, namely [Ru(bpy) 3 − x (TTF-dppz) x ] 2+ (x = 1 − 3). For x = 2, irradiation into the metal to dppz charge transfer transition results in electron transfer from TTF to ruthenium, thus creating a charge-separated state best described by [(TTF + -dppz)Ru(dppz − -TTF)(bpy)] 2+ with a lifetime of 2.5 µ s in dichloromethane.Keywords: Charge-separated states ⋅ Intraligand charge transfer ⋅ Metal-ligand-charge-transfer ⋅ Ruthenium(II)-polypyridine complexes ⋅ Tetrathiafulvalene step is always given by the absorption of a photon, which promotes the chromophore to an electronically and often vibrationally excited state. This initially excited state is most often extremely short-lived, and the system decays via vibrational relaxation, internal conversion, intersystem crossing, luminescence, and energy and electron transfer back to the ground state or via some chemical reaction to a given photochemical product.A key issue of photophysics and photochemistry is the creation of long-lived charge-separated states using so-called donor − acceptor (DA) assemblies, in which the excitation of either the donor to D*A or the acceptor to DA* is followed by the transfer of an electron from D to A to form a state best described by D + A − . As an extension of the simple dyad, the donor and the acceptor may be linked by a photophysically active bridge to afford the triad DBA. In this case, the excitation of the bridge to DB*A results in double electron transfer, namely from the HOMO of D to the SOMO-1 of B* and from the SOMO of B* to the LUMO of A, thus forming a species of the form D + BA − , which in general has a longer lifetime of the charge-separated state than that in the corresponding dyad due to the weaker electronic coupling between D and A. Such triads, composed of tetrathiafulvalene, porphyrins and fullerenes have been successfully used in the creation of artificial photosynthetic systems. [6] Tertrathiafulvalene derivatives, on the one hand, constitute a class of versatile electron donors for a number of interesting applications, [7] in fields such as molecular electronics [8] and in organic conductors and superconductors. [9] Of particular interest in the context of this paper is that they are known to quench the luminescence of almost any chromophore in their vicinity through reductive electron transfer quenching. [10] Ruthenium(ii) polypyridine complexes, on the other hand, are known not only for the luminescence from metal-to-ligand-chargetransfer (MLCT) states but also for their use as sensitizers for light-induced electron transfer in solar ene...

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“…The reaction of 2 7 with AcOH and protection of N-H group by tosyl group gave imidazole-annelated benzo-1,3-dithiole-2-thione 3. The cross-coupling reaction between 3 and 4,5-bis(n-propylthio)-1,3-dithiole-2-one (4) 7 using P(OEt) 3 followed by the treatment with KOH yielded 1. The alternative preparation of 1 was performed by the imidazole-ring formation of 5 which was prepared from 2 and 4.…”

mentioning

confidence: 99%

“…The alternative preparation of 1 was performed by the imidazole-ring formation of 5 which was prepared from 2 and 4. 7 The former procedure is preferable for the chemical modification on TTF skeleton, while the latter is more convenient for the introduction of substituent groups into imidazole ring by using various carboxylic acids. As expected, insertion of benzene ring resulted in good air-stability of 1.…”

mentioning

confidence: 99%

A Novel TTF-based Electron-donor with Imidazole-annelation Having Hydrogen-bonding and Proton-transfer Abilities

Yamamoto¹,

Yakiyama²,

Murata³

et al. 2007

Chemistry Letters

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A TTF derivative with an imidazole-annelation having hydrogen-bond and proton-donor/acceptor abilities was newly synthesized. The donor formed a two-dimensional structure by hydrogen-bonds and stacks in the crystal. The imidazoleannelation increased the electron-donating ability of the donor.Tetrathiafulvalene (TTF) system, a strong electron donor giving a stable radical cation species, has been intensively studied in the research fields of organic conductors 1 and moleculebased electronic materials.2 In the recent study of TTF chemistry, introduction of hydrogen-bond (H-bond) interaction has provided important strategies for molecular design to control molecular arrangement in charge-transfer (CT) complexes and salts. Furthermore, the cooperation between CT and proton-transfer (PT) at H-bond site has served as an attractive phenomena in the development of exotic molecule-based materials. 4 Our recent study for CT complexes of an imidazole-substituted TTF derivative (TTF-Im) has disclosed the electronic and structural modulation effects of H bonds to achieve highly conducting CT complexes.5 Furthermore, the PT ability of imidazole moiety demonstrated simultaneous CT and PT complexes. 5b To enhance the cooperation between CT on TTF and PT on imidazole moieties, an integration of the -electronic systems of both TTF and imidazole moieties is preferable. In this respect, we have designed and synthesized a novel -extended

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An Experimental and Computational Study on Intramolecular Charge Transfer: A Tetrathiafulvalene‐Fused Dipyridophenazine Molecule

Cited by 179 publications

References 48 publications

A Compact Tetrathiafulvalene–Benzothiadiazole Dyad and Its Highly Symmetrical Charge‐Transfer Salt: Ordered Donor π‐Stacks Closely Bound to Their Acceptors

A Compact Tetrathiafulvalene–Benzothiadiazole Dyad and Its Highly Symmetrical Charge‐Transfer Salt: Ordered Donor π‐Stacks Closely Bound to Their Acceptors

Dual Luminescence and Long-Lived Charge-Separated States in Donor-Acceptor Assemblies Based on Tetrathiafulvalene-Fused Ruthenium(II)-Polypyridine Complexes

A Novel TTF-based Electron-donor with Imidazole-annelation Having Hydrogen-bonding and Proton-transfer Abilities

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