Synthetic Approaches to Mixed-Valence Chemistry

Brown, David B.; Wrobleski, James T.

doi:10.1007/978-94-009-9076-0_3

Cited by 8 publications

(7 citation statements)

References 30 publications

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“…The statistical term ((RT/F) ln 2; 36 mV at 298 K, 28 mV at 233 K) due to the presence of two redox sites operates in all cases [67]. It seems reasonable to attribute closely comparable electrostatic/solvation terms to K c for all the present M 2 P 2 compounds, given their geometrical and chemical similarity.…”

Section: Optical/electrochemical Correlations For M 2 Pmentioning

confidence: 65%

“…Compared with many dinuclear systems regarded as tests of such a phenomenon, the present splittings of less than 100 mV would be considered to be very small and near the limit where the rings could be said to be non-interacting, apart from statistical and Coulombic effects [67]. We discuss this point in detail below.…”

Section: Voltammetrymentioning

confidence: 93%

“…The voltammetric separation of the [M 2 P 2 ] 0/1À and [M 2 P 2 ] 1À/2À couples is notably small for all the homobimetallic systems in Table 2, implying comproportionation constant K c values between 4 (pure statistical control [67]) and 10 2 (equation (1)):…”

Section: Optical/electrochemical Correlations For M 2 Pmentioning

confidence: 99%

“…At first sight the small voltammetric gap ( 100 mV) is disconcerting, because it is widely assumed that well-developed electronic coupling in binuclear systems is inextricably linked with large separation in the successive couples [67,77]. If the orbital occupation energy or resonance energy (H ab ) that we associate with the (p u *) 1 configuration for [M 2 P 2 ] 1À dominated the system, this alone would represent a 280 mV splitting in the couples (n 1 /2 = 2250 cm À1 ), which does not eventuate.…”

Section: Optical/electrochemical Correlations For M 2 Pmentioning

confidence: 99%

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Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C₄)[M(OEP)]}(M₂≡H₄, Co₂, Ni₂, Cu₂, Zn₂, Pd₂, Pt₂, Co/Ni, Ni

Arnold

Heath

James

1999

J. Porphyrins Phthalocyanines

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A series of derivatives M 2 P 2 ( M 2 ≡ H 4, Co 2, Ni 2, Cu 2, Zn 2, Pd 2, Pt 2, Co / Ni , Ni / Cu , Ni / Zn ) of the ligand meso,meso′-bis(octaethylporphyrinyl)butadiyne has been prepared and characterized by 1 H NMR, FT Raman and visible absorption spectroscopies as well as by cyclic and a.c. voltammetry in CH 2 Cl 2 solution at 20 and −40 °C. The electronic spectra exhibit multiple Soret bands and the voltammetry reveals successive one-electron reductions indicating the accessibility of ‘mixed valence’ π-radical anions and π-dianions. Using in situ thin layer spectroelectrochemistry, the UV to near-IR spectra of [ M 2 P 2]1− and [ M 2 P 2]2− ( M as above) were recorded at ≤ −40 °C. Apart from the Co complexes (reduced at the metal ion), the bis(porphyrin) anions have spectra which include sharp, intense near-IR bands (ε = 50 000–200 000 M−1cm−1) at c. 4500 and 11 500 cm−1([ M 2 P 2]1−) and 9500 cm−1([ M 2 P 2]2−). An empirically constructed semiquantitative frontier orbital model explains the observed electronic absorption bands. Inter-porphyrin conjugation, mediated by the butadiyne bridge, is responsible for the Soret band multiplicity. The near-IR bands of the anions are assigned to long-axis polarized π → π* transitions within the newly occupied upper manifold of the two-porphyrin eight-orbital framework. The small comproportionation constants found for the diporphyrin monoanions contradict the usual assumption that electronically coupled dimers should have a large voltammetric separation between the first and second redox steps.

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Section: Optical/electrochemical Correlations For M 2 Pmentioning

confidence: 65%

Section: Voltammetrymentioning

confidence: 93%

Section: Optical/electrochemical Correlations For M 2 Pmentioning

confidence: 99%

Section: Optical/electrochemical Correlations For M 2 Pmentioning

confidence: 99%

See 2 more Smart Citations

Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C₄)[M(OEP)]}(M₂≡H₄, Co₂, Ni₂, Cu₂, Zn₂, Pd₂, Pt₂, Co/Ni, Ni

Arnold

Heath

James

1999

J. Porphyrins Phthalocyanines

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“…As for microemulsion synthesis and micelle synthesis, despite the narrow size distribution and well-controlled morphology, one main drawback is that many poisonous wastes may be produced from the large amount of solvent used. 24…”

Section: Introductionmentioning

confidence: 99%

Synthesis of magnetic Fe₃O₄ micro/nanospheres in organic solvent

Hui‐min

Wang

Tan

et al. 2018

Journal of Applied Biomaterials & Functional Materials

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Introduction: Micro/nanostructured materials have attracted a great deal of attention, and many strategies have been developed to fabricate micro/nanostructured materials. Methods: Amine-functionalized micro/nanostructured Fe 3 O 4 with different sizes was synthesized conveniently in organic media. The chemical structures of as-synthesized products were characterized by FTIR, TEM, SEM, and XRD. Results: The ligand binds to the Fe 3 O 4 core by hydrogen bond between the oxygen atom on the surface of Fe 3 O 4 and the hydrogen atom in molecular ethylenediamine. Their magnetic properties were also investigated. Conclusions: First, there is no need to control the reaction under a nitrogen atmosphere, and just one salt is used as an iron source. The growth and the surface modification of Fe 3 O 4 crystalline nucleation happen at the same time. Second, monodispersed Fe 3 O 4 micro/nanospheres were prepared without additional surfactant or external magnetic fields. Third, this method is preferred compared with the conventional organic phase method, as the reaction condition is milder and less pollutant will be produced.

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A Personal Account on Inorganic Reaction Mechanisms

Polaczek,

Kieca,

Oszajca

et al. 2023

The Chemical Record

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The presented Review is focused on the latest research in the field of inorganic chemistry performed by the van Eldik group and his collaborators. The first part of the manuscript concentrates on the interaction of nitric oxide and its derivatives with biologically important compounds. We summarized mechanistic information on the interaction between model porphyrin systems (microperoxidase) and NO as well as the recent studies on the formation of nitrosylcobalamin (CblNO). The following sections cover the characterization of the Ru(II)/Ru(III) mixed‐valence ion‐pair complexes, including Ru(II)/Ru(III)(edta) complexes. The last part concerns the latest mechanistic information on the DFT techniques applications. Each section presents the most important results with the mechanistic interpretations.

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Synthetic Approaches to Mixed-Valence Chemistry

Cited by 8 publications

References 30 publications

Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C₄)[M(OEP)]}(M₂≡H₄, Co₂, Ni₂, Cu₂, Zn₂, Pd₂, Pt₂, Co/Ni, Ni

Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C₄)[M(OEP)]}(M₂≡H₄, Co₂, Ni₂, Cu₂, Zn₂, Pd₂, Pt₂, Co/Ni, Ni

Synthesis of magnetic Fe₃O₄ micro/nanospheres in organic solvent

A Personal Account on Inorganic Reaction Mechanisms

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Synthetic Approaches to Mixed-Valence Chemistry

Cited by 8 publications

References 30 publications

Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C4)[M(OEP)]}(M2≡H4, Co2, Ni2, Cu2, Zn2, Pd2, Pt2, Co/Ni, Ni

Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C4)[M(OEP)]}(M2≡H4, Co2, Ni2, Cu2, Zn2, Pd2, Pt2, Co/Ni, Ni

Synthesis of magnetic Fe3O4 micro/nanospheres in organic solvent

A Personal Account on Inorganic Reaction Mechanisms

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Product

Resources

About

Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C₄)[M(OEP)]}(M₂≡H₄, Co₂, Ni₂, Cu₂, Zn₂, Pd₂, Pt₂, Co/Ni, Ni

Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C₄)[M(OEP)]}(M₂≡H₄, Co₂, Ni₂, Cu₂, Zn₂, Pd₂, Pt₂, Co/Ni, Ni

Synthesis of magnetic Fe₃O₄ micro/nanospheres in organic solvent