Crystal and molecular structure of the paramagnetic 1:1 decamethylferrocenium 7,7,8,8-tetracyano-p-quinodimethanide dimer salt: {[Fe(C5Me5)2]+.cntdot.}2(TCNQ)22-

Reis, Arthur H.; Preston, L. D.; Williams, Jack M.; Peterson, S. W.; Candela, G. A.; Swartzendruber, L. J.; Miller, Joel S.

doi:10.1021/ja00504a058

Cited by 59 publications

(27 citation statements)

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“…For example, molecule A is surrounded by eight [FeCp* 2 ] + units with ten intermolecular N⋅⋅⋅C contacts between 3.36 and 3.61 Å (Figure 6 b; for molecule B , see the Supporting Information). The average FeC bond lengths of 2.097 Å, based on the three ordered [FeCp* 2 ] + units, are consistent with the presence of Fe III atoms 37…”

Section: Resultssupporting

confidence: 59%

“…The average Fe À C bond lengths of 2.097 , based on the three ordered [FeCp* 2 ] + units, are consistent with the presence of Fe III atoms. [37] Naturally, the s-bond formation between two radical centers results in disappearance of paramagnetic properties. In analogy to the reported TCNQ s-dimers, the central C À C bond in diamagnetic [12] 2 2À is expected to be rather weak due to the long bond length, considerable delocalization of Moreover, the solid obtained upon evaporation of the CHCl 3 solution gave identical IR spectrum to that of pristine 15.…”

Section: Slopementioning

confidence: 99%

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Organic Super‐Acceptors with Efficient Intramolecular Charge‐Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F₄‐TCNQ to Donor‐Substituted Cyanoalkynes

Kivala

Boudon

Gisselbrecht

et al. 2009

Chemistry A European J

134

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Rivaling the best one: Thermal [2+2] cycloadditions of TCNE, TCNQ, and F(4)-TCNQ to N,N-dimethylanilino-substituted cyanoalkynes afforded a new class of organic super-acceptors featuring efficient intramolecular charge-transfer interactions. These acceptors rival the acceptor F(4)-TCNQ in the propensity for reversible electron uptake as well as in electron affinity (see figure), which makes them interesting as p-type dopants for potential application in optoelectronic devices.Thermal [2+2] cycloadditions of tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)-TCNQ) to N,N-dimethylanilino-substituted (DMA-substituted) alkynes bearing either nitrile, dicyanovinyl (DCV; -CH==C(CN)(2)), or tricyanovinyl (TCV; -C(CN)==C(CN)(2)) functionalities, followed by retro-electrocyclization, afforded a new class of stable organic super-acceptors. Despite the nonplanarity of these acceptors, as revealed by X-ray crystallographic analysis and theoretical calculations, efficient intramolecular charge-transfer (CT) interactions between the DMA donors and the CN-containing acceptor moieties are established. The corresponding CT bands appear strongly bathochromically shifted with maxima up to 1120 nm (1.11 eV) accompanied by an end-absorption in the near infrared around 1600 nm (0.78 eV) for F(4)-TCNQ adducts. Electronic absorption spectra of selected acceptors were nicely reproduced by applying the spectroscopy oriented configuration interaction (SORCI) procedure. The electrochemical investigations of these acceptors by cyclic voltammetry (CV) and rotating disc voltammetry (RDV) in CH(2)Cl(2) identified their remarkable propensity for reversible electron uptake rivaling the benchmark compounds TCNQ (E(red,1)=-0.25 V in CH(2)Cl(2) vs. Fc(+)/Fc) and F(4)-TCNQ (E(red,1)=+0.16 V in CH(2)Cl(2) vs. Fc(+)/Fc). Furthermore, the electron-accepting power of these new compounds expressed as adiabatic electron affinity (EA) has been estimated by theoretical calculations and compared to the reference acceptor F(4)-TCNQ, which is used as a p-type dopant in the fabrication of organic light-emitting diodes (OLEDs) and solar cells. A good linear correlation exists between the calculated EAs and the first reduction potentials E(red,1). Despite the substitution with strong DMA donors, the predicted EAs reach the value calculated for F(4)-TCNQ (4.96 eV) in many cases, which makes the new acceptors interesting for potential applications as dopants in organic optoelectronic devices. The first example of a charge-transfer salt between the DMA-substituted TCNQ adduct (E(red,1)=-0.27 V vs. Fc(+)/Fc) and the strong electron donor decamethylferrocene ([FeCp*(2)]; Cp*=pentamethylcyclopentadienide; E(ox,1)=-0.59 V vs. Fc(+)/Fc) is described. Interestingly, the X-ray crystal structure showed that in the solid state the TCNQ moiety in the acceptor underwent reductive sigma-dimerization upon reaction with the donor.

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Section: Resultssupporting

confidence: 59%

Section: Slopementioning

confidence: 99%

Organic Super‐Acceptors with Efficient Intramolecular Charge‐Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F₄‐TCNQ to Donor‐Substituted Cyanoalkynes

Kivala

Boudon

Gisselbrecht

et al. 2009

Chemistry A European J

134

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“…By using a metal ion and creating a charge transfer salt with an organic radical acting as the anion, the organic can act as an exchange pathway between magnetic ions. 1,2 One of the first examples of charge transfer magnetic materials was the metallocene-TCNQ (7,7,8,8- 3,4 A further advancement in metal-organic magnetism was with the synthesis of the M(TCNQ) 2 series, where M ¼ Fe, Mn, Co, and Ni. 5 These new compounds were unsolvated and there was clear evidence of crystallinity from x-ray diffraction data where the unit cell was predicted to be tetragonal.…”

mentioning

confidence: 99%

A muon spin relaxation study of the metal-organic magnet Ni(TCNQ)2

Berlie

Terry

Giblin

et al. 2013

Journal of Applied Physics

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“…The ease of the one-electron oxidation of metallocene derivatives is confirmed by the formation of paramagnetic salts, where the anionic component may consist of the radical-anion derived from the organic one-electron acceptor tetracyanoquinodimethane (TCNQ) [56]. Such salts are in essence organometallic analogues of charge transfer complexes [57].…”

Section: Anion and Cation Radicals Formed In Metallocenesmentioning

confidence: 99%

Radical Mechanisms in the Metallocenes

Çalişkan¹

2017

Recent Progress in Organometallic Chemistry

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A special class of sandwich complexes is the metallocenes. The best-known members are the metallocenes of the formula M(C 5 H 5) 2 , where M = zirconium, zinc, titanium, hafnium, vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, osmium, cobalt, rhodium, and nickel. Besides the two cyclopentadienyl rings, the metal can have additional ligands depending on its valence state. These species are also called bis(cyclopentadienyl)metal complexes. Bis(cyclopentadienyl) complexes are called metallocenes or sandwich compounds. Metal-centred radical and cyclopentadienyl radical structures can occur in the metallocene. The anion and cation radicals can also be formed by charge transfer transition.

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Crystal and molecular structure of the paramagnetic 1:1 decamethylferrocenium 7,7,8,8-tetracyano-p-quinodimethanide dimer salt: {[Fe(C5Me5)2]+.cntdot.}2(TCNQ)22-

Cited by 59 publications

References 0 publications

Organic Super‐Acceptors with Efficient Intramolecular Charge‐Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F₄‐TCNQ to Donor‐Substituted Cyanoalkynes

Organic Super‐Acceptors with Efficient Intramolecular Charge‐Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F₄‐TCNQ to Donor‐Substituted Cyanoalkynes

A muon spin relaxation study of the metal-organic magnet Ni(TCNQ)2

Radical Mechanisms in the Metallocenes

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Crystal and molecular structure of the paramagnetic 1:1 decamethylferrocenium 7,7,8,8-tetracyano-p-quinodimethanide dimer salt: {[Fe(C5Me5)2]+.cntdot.}2(TCNQ)22-

Cited by 59 publications

References 0 publications

Organic Super‐Acceptors with Efficient Intramolecular Charge‐Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F4‐TCNQ to Donor‐Substituted Cyanoalkynes

Organic Super‐Acceptors with Efficient Intramolecular Charge‐Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F4‐TCNQ to Donor‐Substituted Cyanoalkynes

A muon spin relaxation study of the metal-organic magnet Ni(TCNQ)2

Radical Mechanisms in the Metallocenes

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Organic Super‐Acceptors with Efficient Intramolecular Charge‐Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F₄‐TCNQ to Donor‐Substituted Cyanoalkynes

Organic Super‐Acceptors with Efficient Intramolecular Charge‐Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F₄‐TCNQ to Donor‐Substituted Cyanoalkynes