[V16O38(CN)]9–: A Soluble Mixed-Valence Redox-Active Building Block with Strong Antiferromagnetic Coupling

2012 ◽  
Vol 51 (17) ◽  
pp. 9192-9199 ◽  
Author(s):  
Tony D. Keene ◽  
Deanna M. D’Alessandro ◽  
Karl W. Krämer ◽  
Jason R. Price ◽  
David J. Price ◽  
...  
Keyword(s):  
Building Block ◽  
Mixed Valence ◽  
Antiferromagnetic Coupling ◽  
Redox Active

ChemInform Abstract: [V16O38(CN)]9-: A Soluble Mixed-Valence Redox-Active Building Block with Strong Antiferromagnetic Coupling.

ChemInform ◽  
2012 ◽  
Vol 43 (45) ◽  
pp. no-no
Author(s):  
Tony D. Keene ◽  
Deanna M. D'Alessandro ◽  
Karl W. Kraemer ◽  
Jason R. Price ◽  
David J. Price ◽  
...  
Keyword(s):  
Building Block ◽  
Mixed Valence ◽  
Antiferromagnetic Coupling ◽  
Redox Active

Mixed-valence molecular magnets based on building block: Structures, magnetic properties and DFT analyses

Polyhedron ◽  
2007 ◽  
Vol 26 (9-11) ◽  
pp. 1781-1786 ◽  
Author(s):  
Y.C. Chen ◽  
G.X. Liu ◽  
P.F. Wang ◽  
H. Xu ◽  
X.M. Ren ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Building Block ◽  
Mixed Valence ◽  
Molecular Magnets ◽  
Block Structures

scholarly journals Pyramidal Heteroanion-Directed and Reduced MoV-Driven Assembly of Multi-Layered Polyoxometalate Cages

2018 ◽  
Author(s):  
Qi Zheng, ◽  
Manuel Kupper ◽  
Weimin Xuan ◽  
Hirofumi Oki ◽  
Ryo Tsunashima ◽  
...  
Keyword(s):  
Self Assembly ◽  
Electronic Materials ◽  
Electronic Devices ◽  
Mixed Valence ◽  
The Self ◽  
Model Structure ◽  
Redox Titration ◽  
Metal Centers ◽  
Redox Active ◽  
Tetrabutyl Ammonium

The fabrication of redox-active polyoxometalates (POMs) that can switch between multiple states is critical for their application in electronic devices, yet, a sophisticated synthetic methodology is not well developed for such cluster types. Here we describe the heteroanion-directed and reduction-driven assembly of a series of multi-layered POM cages 1-10 templated by 1-3 redox-active pyramidal heteroanions. The heteroanions greatly affect the selfassembly of the resultant POM cages, leading to the generation of unprecedented three-layered peanut-shaped - 4, 7 and 8 - or bulletshaped - 5 and 6 - structures. The introduction of reduced molybdate is essential for the self-assembly of the compounds and results in mixed-metal (W/Mo), and mixed-valence (WVI/MoV) 1-10, as confirmed by redox titration, UV-Vis-NIR, NMR spectroscopy and mass spectrometry. 11, the tetrabutyl ammonium (TBA) salt derivative of the fully oxidized 3, is produced as a model structure for measurements to confirm that 1-10 are a statistical mixture of isostructural clusters with different ratios of W/Mo. Finally, multilayered POM cages exhibit dipole relaxations due to the presence of mixed valence WVI/MoV metal centers, demonstrating their potential uses for electronic materials.

scholarly journals Generation of Bis(ferrocenyl)silylenes from Siliranes

Molecules ◽  
2020 ◽  
Vol 25 (24) ◽  
pp. 5917
Author(s):  
Yang Pan ◽  
Shogo Morisako ◽  
Shinobu Aoyagi ◽  
Takahiro Sasamori
Keyword(s):  
Transition Metal ◽  
Building Block ◽  
Building Blocks ◽  
Redox Behavior ◽  
Organosilicon Compounds ◽  
Design And Synthesis ◽  
Mild Conditions ◽  
Redox Active ◽  
Electronic Perturbation ◽  
Active Transition

Divalent silicon species, the so-called silylenes, represent attractive organosilicon building blocks. Isolable stable silylenes remain scarce, and in most hitherto reported examples, the silicon center is stabilized by electron-donating substituents (e.g., heteroatoms such as nitrogen), which results in electronic perturbation. In order to avoid such electronic perturbation, we have been interested in the chemistry of reactive silylenes with carbon-based substituents such as ferrocenyl groups. Due to the presence of a divalent silicon center and the redox-active transition metal iron, ferrocenylsilylenes can be expected to exhibit interesting redox behavior. Herein, we report the design and synthesis of a bis(ferrocenyl)silirane as a precursor for a bis(ferrocenyl)silylene, which could potentially be used as a building block for redox-active organosilicon compounds. It was found that the isolated bis(ferrocenyl)siliranes could be a bottleable precursor for the bis(ferrocenyl)silylene under mild conditions.

Ligand mixed-valence and electrical conductivity in coordination complexes containing a redox-active phenalenol-substituted ligand

2019 ◽  
Vol 48 (23) ◽  
pp. 8053-8056 ◽  
Author(s):  
Sarah Dale ◽  
Nico M. Bonanno ◽  
Mark Pelaccia ◽  
Alan J. Lough ◽  
Atsuhiro Miyawaki ◽  
...  
Keyword(s):  
Electrical Conductivity ◽  
Mixed Valence ◽  
Closed Shell ◽  
Coordination Complexes ◽  
Low Energy ◽  
Redox Active

Neutral Fe3+ and Co3+ complexes are reported featuring mixed-valent open- and closed-shell ligands, low energy IVCT bands and electrical conductivity.

scholarly journals Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

2015 ◽  
Vol 11 ◽  
pp. 1596-1613 ◽  
Author(s):  
Masahiko Iyoda ◽  
Masashi Hasegawa
Keyword(s):  
Mixed Valence ◽  
Supramolecular Assembly ◽  
Radical Cations ◽  
Supramolecular Assemblies ◽  
Supramolecular Structures ◽  
Oxidation States ◽  
Face To Face ◽  
Redox Active ◽  
Nanophase Separation ◽  
Self Organizing

The construction of redox-active supramolecular assemblies based on star-shaped and radially expanded tetrathiafulvalene (TTF) oligomers with divergent and extended conjugation is summarized. Star-shaped TTF oligomers easily self-aggregate with a nanophase separation to produce supramolecular structures, and their TTF units stack face-to-face to form columnar structures using the fastener effect. Based on redox-active self-organizing supramolecular structures, conducting nanoobjects are constructed by doping of TTF oligomers with oxidants after the formation of such nanostructures. Although radical cations derived from TTF oligomers strongly interact in solution to produce a mixed-valence dimer and π-dimer, it seems to be difficult to produce nanoobjects of radical cations different from those of neutral TTF oligomers. In some cases, however, radical cations form nanostructured fibers and rods by controlling the supramolecular assembly, oxidation states, and counter anions employed.

scholarly journals Dimers of pyrrolo-annelated indenofluorene-extended tetrathiafulvalenes – large multiredox systems

RSC Advances ◽  
2020 ◽  
Vol 10 (26) ◽  
pp. 15030-15033
Author(s):  
Line Broløs ◽  
Mogens Brøndsted Nielsen
Keyword(s):  
Building Block ◽  
Redox Active

A new pyrrolo-annelated indenofluorene-extended tetrathiafulvalene building block was developed and employed in N-arylation reactions for construction of redox-active dimeric scaffolds.

Redox-Active Heteroacene Chromophores Derived from a Non-Linear Aromatic Diimide

2019 ◽  
Author(s):  
Stella Luo ◽  
Kellie Stellmach ◽  
Stella Ikuzwe ◽  
Dennis Cao
Keyword(s):  
Density Functional Theory ◽  
Nucleophilic Substitution ◽  
Building Block ◽  
Density Functional ◽  
Organic Materials ◽  
Density Functional Theory Calculations ◽  
Differential Pulse ◽  
Fine Tuning ◽  
Functional Theory ◽  
Redox Active

<div>This work describes a three-step chromatography-free protocol for the synthesis of a novel organic materials</div><div>building block, dichlorinated mellophanic diimide (MDI), that is shown to undergo nucleophilic substitution</div><div>with a variety of ortho disubstituted benzenes to yield a series of chromophores. Furthermore, 1,2,4,5-</div><div>tetrasubstituted benzenes can be used to synthesize tetraimide heteropentacene derivatives endcapped by</div><div>MDI motifs. The fine-tuning effects of heteroatom identity were investigated by UV-Vis and fluorescence</div><div>spectroscopy, cyclic and differential pulse voltammetries, and density functional theory calculations. Oxidation</div><div>of diamino MDI derivatives yields di- and tetraimide functionalized azaacenes with significantly lowered LUMO</div><div>levels (down to –4.49 eV), narrowed bandgaps (down to 1.81 eV), and high molar absorptivities (up to 84,000</div><div>M<sup>–1</sup> cm<sup>–1</sup>).</div>

scholarly journals Electrical conductivity in two mixed-valence liquids

2015 ◽  
Vol 17 (21) ◽  
pp. 14107-14114 ◽  
Author(s):  
Wenzhi Yao ◽  
Steven P. Kelley ◽  
Robin D. Rogers ◽  
Thomas P. Vaid
Keyword(s):  
Electrical Conductivity ◽  
Electron Transfer ◽  
Exchange Rate ◽  
Rate Constants ◽  
Room Temperature ◽  
Mixed Valence ◽  
Electrical Current ◽  
Active Species ◽  
Redox Active

Two mixed-valence room-temperature liquids are reported: BuFc–[BuFc+][NTf2−] (BuFc = n-butylferrocene) and TEMPO–[TEMPO+][NTf2−]. Both are conductors of DC electrical current, and their conductivity is modeled based on the electron-transfer self-exchange rate constants of their constituent redox-active species.

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