Dimeric Phenalenyl-Based Neutral Radical Molecular Conductors

2001 ◽  
Vol 123 (17) ◽  
pp. 4041-4048 ◽  
Author(s):  
X. Chi ◽  
M. E. Itkis ◽  
K. Kirschbaum ◽  
A. A. Pinkerton ◽  
R. T. Oakley ◽  
...  
Keyword(s):  
Molecular Conductors ◽  
Neutral Radical

New Family of Aminophenalenyl-Based Neutral Radical Molecular Conductors:  Synthesis, Structure, and Solid State Properties

2005 ◽  
Vol 127 (22) ◽  
pp. 8185-8196 ◽  
Author(s):  
Swadhin K. Mandal ◽  
Mikhail E. Itkis ◽  
Xiaoliu Chi ◽  
Satyabrata Samanta ◽  
David Lidsky ◽  
...  
Keyword(s):  
Solid State ◽  
Molecular Conductors ◽  
Neutral Radical ◽  
New Family

Resonating Valence Bond Ground State in Oxygen-Functionalized Phenalenyl-Based Neutral Radical Molecular Conductors

2006 ◽  
Vol 128 (6) ◽  
pp. 1982-1994 ◽  
Author(s):  
Swadhin K. Mandal ◽  
Satyabrata Samanta ◽  
Mikhail E. Itkis ◽  
Dell W. Jensen ◽  
Robert W. Reed ◽  
...  
Keyword(s):  
Ground State ◽  
Valence Bond ◽  
Molecular Conductors ◽  
Neutral Radical ◽  
Resonating Valence Bond

Phenalenyl-Based Neutral Radical Molecular Conductors:  Substituent Effects on Solid-State Structures and Properties

2007 ◽  
Vol 129 (22) ◽  
pp. 7163-7174 ◽  
Author(s):  
Sushanta K. Pal ◽  
Mikhail E. Itkis ◽  
Fook S. Tham ◽  
Robert W. Reed ◽  
Richard T. Oakley ◽  
...  
Keyword(s):  
Solid State ◽  
Substituent Effects ◽  
Molecular Conductors ◽  
Neutral Radical ◽  
Structures And Properties ◽  
Solid State Structures

Hydrostibination of Alkynes: A Radical Mechanism

2020 ◽  
Author(s):  
Josh MacMillan ◽  
Katherine Marczenko ◽  
Erin Johnson ◽  
Saurabh Chitnis
Keyword(s):  
Density Functional ◽  
Activation Barrier ◽  
Closed Shell ◽  
Reaction Rates ◽  
Radical Mechanism ◽  
Neutral Radical ◽  
Kinetic Isotope ◽  
Rate Limiting Step ◽  
Ionic Mechanisms ◽  
Terminal Acetylenes

The addition of Sb-H bonds to alkynes was reported recently as a new hydroelementation reaction that exclusively yields anti-Markovnikov <i>Z</i>-olefins from terminal acetylenes. We examine four possible mechanisms that are consistent with the observed stereochemical and regiochemical outcomes. A comprehensive analysis of solvent, substituent, isotope, additive, and temperature effects on hydrostibination reaction rates definitively refutes three ionic mechanisms involving closed-shell charged intermediates. Instead the data support a fourth pathway featuring neutral radical Sb<sup>II</sup> and Sb<sup>III</sup> intermediates. Density Functional Theory (DFT) calculations are consistent this model, predicting an activation barrier that is within 1 kcal mol<sup>-1</sup> of the experimental value (Eyring analysis) and a rate limiting step that is congruent with experimental kinetic isotope effect. We therefore conclude that hydrostibination of arylacetylenes is initiated by the generation of stibinyl radicals, which then participate in a cycle featuring Sb<sup>II</sup> and Sb<sup>III</sup> intermediates to yield the observed <i>Z</i>-olefins as products. This mechanistic understanding will enable rational evolution of hydrostibination as a methodology for accessing challenging products such as <i>E</i>-olefins.

Charge transfer in self-assembled monolayers of molecular conductors containing tripodal anchor and terpyridine-metal redox switching element

2021 ◽  
pp. 138302
Author(s):  
Štěpánka Nováková Lachmanová ◽  
František Vavrek ◽  
Táňa Sebechlebská ◽  
Viliam Kolivoška ◽  
Michal Valášek ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Self Assembled Monolayers ◽  
Switching Element ◽  
Molecular Conductors ◽  
Assembled Monolayers ◽  
Self Assembled ◽  
Redox Switching ◽  
Metal Redox

scholarly journals Old Donors for New Molecular Conductors: Combining TMTSF and BEDT-TTF with Anionic (TaF6)1−x/(PF6)x Alloys

Crystals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 386
Author(s):  
Magali Allain ◽  
Cécile Mézière ◽  
Pascale Auban-Senzier ◽  
Narcis Avarvari
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Density Wave ◽  
Spin Density Wave ◽  
Orthorhombic Phase ◽  
Molecular Conductors ◽  
Bechgaard Salts ◽  
Temperature Conductivity ◽  
Room Temperature Conductivity ◽  
Resistivity Measurements

Tetramethyl-tetraselenafulvalene (TMTSF) and bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF) are flagship precursors in the field of molecular (super)conductors. The electrocrystallization of these donors in the presence of (n-Bu4N)TaF6 or mixtures of (n-Bu4N)TaF6 and (n-Bu4N)PF6 provided Bechgaard salts formulated as (TMTSF)2(TaF6)0.84(PF6)0.16, (TMTSF)2(TaF6)0.56(PF6)0.44, (TMTSF)2(TaF6)0.44(PF6)0.56 and (TMTSF)2(TaF6)0.12(PF6)0.88, together with the monoclinic and orthorhombic phases δm-(BEDT-TTF)2(TaF6)0.94(PF6)0.06 and δo-(BEDT-TTF)2(TaF6)0.43(PF6)0.57, respectively. The use of BEDT-TTF and a mixture of (n-Bu4N)TaF6/TaF5 afforded the 1:1 phase (BEDT-TTF)2(TaF6)2·CH2Cl2. The precise Ta/P ratio in the alloys has been determined by an accurate single crystal X-ray data analysis and was corroborated with solution 19F NMR measurements. In the previously unknown crystalline phase (BEDT-TTF)2(TaF6)2·CH2Cl2 the donors organize in dimers interacting laterally yet no organic-inorganic segregation is observed. Single crystal resistivity measurements on the TMTSF based materials show typical behavior of the Bechgaard phases with room temperature conductivity σ ≈ 100 S/cm and localization below 12 K indicative of a spin density wave transition. The orthorhombic phase δo-(BEDT-TTF)2(TaF6)0.43(PF6)0.57 is semiconducting with the room temperature conductivity estimated to be σ ≈ 0.16–0.5 S/cm while the compound (BEDT-TTF)2(TaF6)2·CH2Cl2 is also a semiconductor, yet with a much lower room temperature conductivity value of 0.001 to 0.0025 S/cm, in agreement with the +1 oxidation state and strong dimerization of the donors.

First molecular conductors of BPDT-TTF with metallacarborane anions: (BPDT-TTF)[3,3′-Сr(1,2-C2B9H11)2] and (BPDT-TTF)[3,3′-Сo(1,2-C2B9H11)2] – Synthesis, structure, properties

2018 ◽  
Vol 867 ◽  
pp. 375-380 ◽  
Author(s):  
Olga N. Kazheva ◽  
Denis M. Chudak ◽  
Gennady V. Shilov ◽  
Ekaterina A. Komissarova ◽  
Irina D. Kosenko ◽  
...  
Keyword(s):  
Molecular Conductors ◽  
Structure Properties
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