Synthesis, characterization, and electrochemical study of diiron organometallic derivatives of 2,6-dibutyl-4,8-dimethyl-1,5-dihydro-s-indacene

A new fused ring compound, 2,6-dibutyl-4,8-dimethyl-1,5-dihydro-s-indacene (VII) (H2L), has been synthesized from 2,5-dimethyl-1,4-dibromomethylbenzene in almost quantitative yield. Two organomtallic binuclear complexes, [Cp*Fe-L-FeCp*] (1) and the mixed-valence compound [Cp*Fe-L-FeCp*]+ BF–4 (2), have been characterized by spectroscopic and electrochemical techniques. The cyclic voltammogram of 1 exhibits a potential difference of 668 mV between two redox peaks and the UV-vis-NIR spectra of compound 2 shows an intervalance charge transfer band at 1794 nm. The information gathered by these techniques indicates that the studied binuclear complex has strong interaction between the two metal centres.

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Charge transfer band observed in bismuth mixed-valence oxides, Bi1−xYxO1.5+δ (x = 0.3)

Solid State Communications ◽

10.1016/s0038-1098(97)00405-5 ◽

1997 ◽

Vol 104 (11) ◽

pp. 705-708 ◽

Cited By ~ 21

Author(s):

H. Mizoguchi ◽

H. Kawazoe ◽

H. Hosono ◽

S. Fujitsu

Keyword(s):

Charge Transfer ◽

Charge Transfer Band ◽

Mixed Valence

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121Sb NMR and SCF-MS-Xα Studies of Quadrupole Interaction and The Electronic Structure of Mixed-Valence Compound, Cs2SbCl6

Zeitschrift für Naturforschung A ◽

10.1515/zna-1996-5-651 ◽

1996 ◽

Vol 51 (5-6) ◽

pp. 672-676 ◽

Cited By ~ 4

Author(s):

Takahiro Ueda ◽

Nobuo Nakamura

Keyword(s):

Electronic Structure ◽

Charge Transfer ◽

Ground State ◽

Mixed Valence ◽

Quadrupole Coupling Constant ◽

Coupling Constant ◽

Nmr Spectrum ◽

Quadrupole Coupling ◽

Mixed Valence Compound ◽

Complex Anions

Cs2SbCl6 is known as a typical mixed-valence compound. It crystallizes into a tetragonal space group I41/amd and contains two different complex anions, Sb(III)Cl3-6 and Sb(V)Cl-6 . The dark blue color of this compound has been considered to originate from a charge transfer between the above two anions. In order to study the electronic structure of these complex anions and the existence of charge transfer between them we measured the 121Sb NMR spectrum and carried out molecular orbital calculations on the electronic states of these anions. The 121Sb NMR spectrum consists of two peaks at 0 and 30 kHz which can be assigned to the central transition of 121Sb in Sb(V)Cl-6 and Sb(III)Cl3-6 , respectively. The line shape analyses of the spectra led to nuclear quadrupole coupling constants of nearly zero for Sb(V)Cl-6 and 4.9 ± 0.5 MHz for Sb(III)Cl3-6 at room temperature. The quadrupole coupling constant of 121Sb(III) decreases steadily on heating. The calculations of the electronic ground state energies of both anions were calculated by the MS-Xα molecular orbital method. The calculated charge-transfer band from the A1g state of Sb(III)Cl3-6 to the A1g state of Sb(V)Cl-6 appears at 610 nm and can account for the experimental electronic spectrum, the calculated quadrupole coupling constant in Sb(III)Cl3-6 however is far larger than the experimental one. The contribution of the charge-transferred state to the ground state is negligible and so the temperature dependence of the quadrupole coupling constant of 121Sb(III) is attributed to an anisotropic thermal expansion of the compound.

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A Hexadecanuclear Copper(I)–Copper(II) Mixed-Valence Compound: Structure, Magnetic Properties, Intervalence Charge Transfer, EPR, and NMR

European Journal of Inorganic Chemistry ◽

10.1002/ejic.200700369 ◽

2007 ◽

Vol 2007 (23) ◽

pp. 3695-3700 ◽

Cited By ~ 6

Author(s):

Senjuti De ◽

Shubhamoy Chowdhury ◽

Jnan P. Naskar ◽

Michael G. B. Drew ◽

Rodolphe Clérac ◽

...

Keyword(s):

Magnetic Properties ◽

Charge Transfer ◽

Mixed Valence ◽

Compound Structure ◽

Intervalence Charge Transfer ◽

Mixed Valence Compound

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ChemInform Abstract: OBSERVATION OF AN INTERVALENCE CHARGE-TRANSFER BAND IN A MIXED-VALENCE RUTHENIUM DIMER BRIDGED BY A NONCONJUGATED NITROGEN DONOR LIGAND

Chemischer Informationsdienst ◽

10.1002/chin.198430283 ◽

1984 ◽

Vol 15 (30) ◽

Author(s):

M. J. K. GENO ◽

J. H. DAWSON

Keyword(s):

Charge Transfer ◽

Charge Transfer Band ◽

Mixed Valence ◽

Donor Ligand ◽

Nitrogen Donor Ligand ◽

Nitrogen Donor ◽

Intervalence Charge Transfer

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Neutral-Type One-Dimensional Mixed-Valence Halogen-Bridged Platinum Chain Complexes with Large Charge-Transfer Band Gaps

Inorganic Chemistry ◽

10.1021/acs.inorgchem.5b02980 ◽

2016 ◽

Vol 55 (5) ◽

pp. 2620-2626 ◽

Cited By ~ 7

Author(s):

Ken-ichi Otake ◽

Kazuya Otsubo ◽

Kunihisa Sugimoto ◽

Akihiko Fujiwara ◽

Hiroshi Kitagawa

Keyword(s):

Charge Transfer ◽

Charge Transfer Band ◽

Mixed Valence ◽

Neutral Type ◽

Band Gaps ◽

One Dimensional ◽

Chain Complexes ◽

Large Charge ◽

Platinum Chain

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Synthesis, characterization, redox, and Hg2+ optical ion sensing properties of ferrocenyl-containing maleo- and fumaronitrile derivatives

Canadian Journal of Chemistry ◽

10.1139/cjc-2014-0075 ◽

2014 ◽

Vol 92 (8) ◽

pp. 739-749 ◽

Cited By ~ 2

Author(s):

Michael R. Dahlby ◽

Anatolii A. Purchel ◽

Pavlo V. Solntsev ◽

Gregory T. Rohde ◽

Yuriy V. Zatsikha ◽

...

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Charge Transfer Band ◽

Electrochemical Techniques ◽

Mixed Valence ◽

Reaction Products ◽

Functional Theory ◽

X Ray ◽

X Ray Crystallography ◽

Oxidation Potentials

Mono-((Z)-2-amino-3-((E)-ferrocenylideneamino)butenedinitrile) (1) and bis-((E)-2,3-bis-((E)-ferrocenylideneamino)butenedinitrile) (2) substituted Schiff bases obtained by the reaction between ferrocenecarbaldehyde and diaminomaleonitrile were prepared and characterized by 1H and 13C NMR, IR, and UV-vis-NIR spectroscopy methods, elemental analysis, and X-ray crystallography. Density functional theory and time-dependent density functional theory were used to elucidate the electronic structure and the origin of observed excited states in both compounds. Electrochemical techniques were employed to investigate the possibility for the formation of a mixed-valence state of the iron centers in 2+, which are connected by a conjugated π-system. Two reversible oxidation potentials were observed in cyclic voltammetry, and spectroelectrochemical experiments revealed the presence of a low-energy intervalence charge transfer band in 2+, corresponding to class II of the mixed-valence systems. Both complexes were tested for cation-recognition properties using a variety of main group and transition-metal cations. It was shown that complex 1 can be used as a selective optical sensor in recognition of Hg2+ ions. It was also shown by NMR spectroscopy and X-ray crystallography that one of the final reaction products between Hg2+ ions and complex 1 is 2-ferrocenyl-4,5-dicyanoimidazole (3).

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