Stable π-dimer of a tetrathiafulvalene cation radical encapsulated in the cavity of cucurbit[8]uril

Ziganshinа, Albina Y.; Ko, Young Ho; Jeon, Woo Sung; Kim, Kimoon

doi:10.1039/b316651a

Cited by 186 publications

(140 citation statements)

References 35 publications

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“…In the solid state, neutral TTFs weakly stack to form dimers or columnar structures through S£S and ³³ interactions (A), whereas neutral TTFs easily dissociate in solution. 13 In contrast, ³-extended TTF derivatives and TTFs having amphiphilic properties self-associate even in solution, resulting in the formation of nanostructures. 57 Furthermore, stronger molecular interactions occur in mixed valence (MV) states with strong charge resonance (CR) (B).…”

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“…3,12 However, there are some ambiguities in the reported MV and ³-dimer states of TTFs in solution because the formation of those states are discussed on the basis of various spectroscopic data. 12c, 13 In order to obtain accurate spectroscopic information about the MV and ³-dimer states of TTFs, we prepared 1,8-bis(tetrathiafulvalenyl)naphthalenes 1a1c (Chart 1) as a model system. Since two TTF units are attached at the 1,8-positions of the naphthalene ring in 1a1c, the face-to-face interactions between two TTFs can be determined very easily.…”

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Face-to-Face Dimeric Tetrathiafulvalenes and Their Cation Radical and Dication Species as Models of Mixed Valence and π-Dimer States

Hasegawa

Daigoku

Hashimoto

et al. 2011

Bulletin of the Chemical Society of Japan

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Intramolecular interactions of face-to-face tetrathiafulvalenes (TTFs) in 1,8-bis(tetrathiafulvalenyl)naphthalene frameworks were investigated in neutral and cationic states. From X-ray analysis and NMR spectroscopy on neutral 1,8-bis(tetrathiafulvalenyl)naphthalenes, which exist as a mixture of syn-and anti-isomers in solution, there is steric repulsion between TTF moieties. However, analysis of the cyclic voltammogram (CV) revealed that a strong attractive interaction was present in the cation radical state. Electronic spectra of the cation radical state showed the presence of a mixedvalence (MV) state with a strong charge resonance feature. ESR spectra of the 1,8-bis(tetrathiafulvalenyl)naphthalene cation radical showed a typical signal of an MV state. Furthermore, a ³-dimer, which exhibits pronounced Davydov splitting in the electronic spectra, was formed in the dication state. The observed absorption bands in the electronic spectra were characterized by using quantum chemical calculations of the cation radical and dication species. NMR spectra of both the ³-dimer and tetracation species show either a deshielding effect due to cationic charge or a shielding effect due to diamagnetic ring currents. To our knowledge, this is the first reported example of a 1 H NMR spectrum of TTF ³-dimer.Tetrathiafulvalene (TTF) and its derivatives can be easily oxidized to form stable cation radicals and dications, and these cationic species have been employed extensively in the development of new organic metals, superconductors, and semiconductor devices.

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Face-to-Face Dimeric Tetrathiafulvalenes and Their Cation Radical and Dication Species as Models of Mixed Valence and π-Dimer States

Hasegawa

Daigoku

Hashimoto

et al. 2011

Bulletin of the Chemical Society of Japan

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“…36−39 Further, [n.n]-quinquethiophenophanes and α,ω-bis(quinquethienyl)alkanes have also been studied as π-dimer models. 40,41 More relevant to this study, some intriguing recent reports have also shown that vinyl-linked tritylthiafullvene radicals can form intermolecular dimers 42 that can switch spin with temperature changes in organic solution 43 or via reversible encapsulation in the cavity of a macrocyclic host to stabilize π-dimer form, 44 but a more general strategy for designing organic molecules with stimuliswitchable spin states would be desirable, particularly if this switching is achievable in water to allow for biological applications.…”

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confidence: 99%

An Organic Spin Crossover Material in Water from a Covalently Linked Radical Dyad

2014

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A covalently linked viologen radical cation dyad acts as a reversible thermomagnetic switch in water. Cycling between diamagnetic and paramagnetic forms by heating and cooling is accompanied by changes in optical and magnetic properties with high radical fidelity. Thermomagnetic switches in water may eventually find use as novel biological thermometers and in temperature-responsive organic materials where the changes in properties originate from a change in electronic spin configuration rather than a change in structure. DisciplinesOrganic Chemistry | Other Chemistry | Physical Chemistry CommentsReprinted (adapted) with permission from J. Org. Chem., 2014, 79 (16) ABSTRACT: A covalently linked viologen radical cation dyad acts as a reversible thermomagnetic switch in water. Cycling between diamagnetic and paramagnetic forms by heating and cooling is accompanied by changes in optical and magnetic properties with high radical fidelity. Thermomagnetic switches in water may eventually find use as novel biological thermometers and in temperature-responsive organic materials where the changes in properties originate from a change in electronic spin configuration rather than a change in structure.C

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“…31,32 Furthermore, the oxidized form of derivative 3 exhibited a strong absorption band with a maximum at 760 nm. According to the literature, 33 the UV-vis absorption at around 760 nm is assigned to a dimer structure of the mono-oxidized TTF moieties. Therefore, the oxidation of derivative 3 caused the formation of a stacked structure of the TTF moieties in solution.…”

Section: Chemical Oxidation Of Ttf Moietiesmentioning

confidence: 99%

Physical and electrical characteristics of supramolecular polymer films based on guanosine derivatives modified with tetrathiafulvalene moiety

Choi

Kuwabara

Kanbara

2012

Polym J

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Supramolecular films consisting of guanosine derivatives modified with a tetrathiafulvalene (TTF) moiety have been prepared. The hydrogen bonding network of the guanosine unit enables the formation of a robust and self-supporting cast film by a solution process. Differential scanning calorimetry and dynamic mechanical analysis (DMA) revealed that the self-supporting films were mechanically flexible and their glass transition temperature was lower than room temperature. The results of the DMA also showed the viscoelastic properties of the films at room temperature. The physical properties of the films of the derivatives depended on both the length of the alkyl chains and the structure of their terminal group. The chemical oxidation of the derivatives resulted in the formation of the absorption band due to the radical cationic TTF moiety. The composite film of the derivatives with 7,7,8,8,-tetracyanoquinodimethane exhibited electrical conductivity.

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Stable π-dimer of a tetrathiafulvalene cation radical encapsulated in the cavity of cucurbit[8]uril

Abstract: The first stable pi-dimer of a tetrathiafulvalene (TTF) cation radical encapsulated in the cavity of cucurbit[8]uril has been isolated at room temperature and fully characterized; it shows absorption bands at 400, 540 and 760 nm, characteristic of the TTF cation radical dimer.

Cited by 186 publications

References 35 publications

Face-to-Face Dimeric Tetrathiafulvalenes and Their Cation Radical and Dication Species as Models of Mixed Valence and π-Dimer States

Face-to-Face Dimeric Tetrathiafulvalenes and Their Cation Radical and Dication Species as Models of Mixed Valence and π-Dimer States

An Organic Spin Crossover Material in Water from a Covalently Linked Radical Dyad

Physical and electrical characteristics of supramolecular polymer films based on guanosine derivatives modified with tetrathiafulvalene moiety

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