Mixed valence cations. Chemistry of .pi.-bridged analogues of biferrocene and biferrocenylene

LeVanda, Carole; Bechgaard, K.; Cowan, Dwaine O.

doi:10.1021/jo00878a008

Cited by 203 publications

(142 citation statements)

References 7 publications

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“…[6,25,[46][47][48][49][50][51][52][53] The energetic position and exclusive occurrence in the mixed-valent systems Fc 2 C + and (FcEt) 2 C + suggest an IVCT character of these low-energy transitions. In our calculations, however, the charge and spin are fully delocalized and the electronic transitions do not involve any charge transfer between the two units.…”

Section: Discussionmentioning

confidence: 99%

Electronic Structure and Absorption Spectra of Biferrocenyl and Bisfulvalenide Diiron Radical Cations: Detection and Assignment of New Low‐Energy Transitions

Warratz

Aboulfadl

Bally

et al. 2009

Chemistry A European J

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New transitions: Low‐energy electronic transitions have been detected spectroscopically in the FeII–FeIII mixed‐valent biferrocenyl radical cation, but are absent in the spectra of the neutral analogue. They have been assigned by time‐dependent DFT calculations (squares in figure). Analogous investigations were performed for the bisfulvalenide FeII–FeIII radical cation.magnified imageUV‐visible/near‐IR (NIR)/mid‐IR (MIR) solution, solid‐state, and matrix‐isolation electronic absorption spectra of the FeII–FeIII mixed‐valent homobimetallic compounds biferrocenyl triiodide (1) and 1′,1′′′‐diethylbiferrocenyltriiodide (2) reveal the presence of a low‐energy transition in the MIR region that has not been reported before. The new absorption feature and the known NIR band are both assigned to intervalence charge‐transfer (IVCT) transitions. To obtain insight into the electronic structures of 1 and 2, DFT calculations with the BP86 functionals and different basis sets have been performed. Based on the molecular orbital scheme of cation 1, one band corresponds to the transition between the highest occupied d orbitals on the two iron centers, whereas the other one is assigned to a transition from a lower‐lying d orbital to the d orbital. For comparison, the doubly bridged bisfulvalenide diiron cation (3) has been investigated by optical absorption spectroscopy and DFT calculations. The experimental and theoretical results are discussed with respect to the degree of electron localization/delocalization in these systems.

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Section: Discussionmentioning

confidence: 99%

Electronic Structure and Absorption Spectra of Biferrocenyl and Bisfulvalenide Diiron Radical Cations: Detection and Assignment of New Low‐Energy Transitions

Warratz

Aboulfadl

Bally

et al. 2009

Chemistry A European J

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“…Moreover, it was expected that the communication between the two metallic centers of dimer complexes having a bridged acetylenic linkage would be greater than that between metallic centers linked by a bridging butadiyne. Indeed, biferrocenyl derivatives bridged by acetylenic linkages Fc-C≡C-Fc and Fc-C≡C-C≡C-Fc have already been described and showed similar cyclic voltammograms with ∆E p 130 and 100 mV, respectively 12,13 . Since ∆E values for the two compounds reported herein are the same, 520mV, these compounds should be the same.…”

Section: Cyclic Voltammetric Analysis Of [Cis-{rucl (Bpy) 2 (M-c≡c-)}mentioning

confidence: 86%

“…This is in agreement with the fact that the pyridine groups of each ligand are not magnetically equivalent and both cis and trans configurations probably would be present. Moreover, in these complexes, the 13 C NMR signals of the Ru-C≡C-carbons are masked by the signals of pyridyl carbons.…”

Section: H and 13 C{ H} Nmr Spectramentioning

confidence: 99%

Synthesis and electrochemical characterization of bimetallic ruthenium complexes with the bridging eta2(<FONT FACE=Symbol>s,s</FONT>)-1,3-butadiyne-1,4-diyl ligand

Stein¹,

Oki²,

Vichi³

2000

J. Braz. Chem. Soc.

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ºC-)}] 2 (1) foi obtido pelo tratamento de 1 equive de 1,4-bis(trimetilsilil)-1,3-butadiino ou bis(trimetilsilil)acetileno com 2 equiv do complexo cis-[RuCl2(bpy)2].2H2O, NaF e NaBF4na mistura de solventes metanol/CH2Cl2 (10/1) com rendimentos de 52% e 35%, respectivamente. Análises de RMN de ¹H, 13C{H} e principalmente eletroquímica, confirmaram que o mesmo produto foi obtido dos dois métodos. Análise de (1) através de voltametria cíclica, no intervalo de potencial de 0 a 1,20 V mostrou dois picos de oxidação quasi-reversíveis referentes ao par redox Ru(II)/Ru(III). Os dois processos redox são separados por 520 V, indicando comunicação eletrônica significante entre os dois centros metálicos]]>

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“…In the past three decades, various atom-bridged diferrocenyl derivatives [1][2][3][4][5] , such as the C, Si, P, Ga, Hg and chalcogen (S, Se and Te) bridged diferrocenes 6 , have been prepared due to their potential applications in magnetic, electronic and optical devices [7][8][9] . The current research interests were concentrated not only on how to construct these atom-bridged differrocene systems, but also on the electrochemical interaction between the two ferrocenyl units.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structure and Electrochemistry of Carbon-Bridged Diferrocenyl Compounds

Xie¹,

Han²,

Zhu³

et al. 2013

Asian J. Chem.

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Mixed valence cations. Chemistry of .pi.-bridged analogues of biferrocene and biferrocenylene

Cited by 203 publications

References 7 publications

Electronic Structure and Absorption Spectra of Biferrocenyl and Bisfulvalenide Diiron Radical Cations: Detection and Assignment of New Low‐Energy Transitions

Electronic Structure and Absorption Spectra of Biferrocenyl and Bisfulvalenide Diiron Radical Cations: Detection and Assignment of New Low‐Energy Transitions

Synthesis and electrochemical characterization of bimetallic ruthenium complexes with the bridging eta2(<FONT FACE=Symbol>s,s</FONT>)-1,3-butadiyne-1,4-diyl ligand

Synthesis, Crystal Structure and Electrochemistry of Carbon-Bridged Diferrocenyl Compounds

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