π-Bonded molecular wires: self-assembly of mixed-valence cation-radical stacks within the nanochannels formed by inert tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anions

CrystEngComm ◽  
2013 ◽  
Vol 15 (48) ◽  
pp. 10638 ◽  
Author(s):  
Sergiy V. Rosokha ◽  
Charlotte L. Stern ◽  
Jeremy T. Ritzert
Keyword(s):  
Self Assembly ◽  
Mixed Valence ◽  
Cation Radical ◽  
Molecular Wires

Electrically-Induced Mixed Valence Causes Resistive Switching in Copper Helical Metallopolymers

2020 ◽  
Author(s):  
Jake L. Greenfield ◽  
Daniele Di Nuzzo ◽  
Emrys Evans ◽  
Satyaprasad P. Senanayak ◽  
Sam Schott ◽  
...  
Keyword(s):  
Self Assembly ◽  
Double Helix ◽  
Mixed Valence ◽  
Fold Increase ◽  
Electrical Current ◽  
Structural Rearrangement ◽  
Molecular Wires ◽  
Coordination Geometry ◽  
Valence Structure ◽  
High Level

<div>Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here we use a bottom-up approach to demonstrate resistive</div><div>switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When we expose the material to an electric field, we determine that approximately 25% of the copper atoms oxidise from Cu(I) to Cu(II) without rupture of the polymer chain. The ability to sustain such high level of oxidation is unprecedented in a copper-based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by Cu(II).</div><div>This mixed-valence structure exhibits a 10<sup>4</sup>-fold increase in</div><div>conductivity, which is projected to last over 10 years. We explain the increase in conductivity as being promoted by the creation, upon oxidation, of partly filled d<sub>z</sub><sup>2</sup></div><div>orbitals aligned along the mixed-valence copper array; the long-lasting nature of the change in conductivity is due to the structural rearrangement of the double-helix, which poses an energetic barrier to re-reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale.</div>

scholarly journals Electrically-Induced Mixed Valence Causes Resistive Switching in Copper Helical Metallopolymers

2020 ◽  
Author(s):  
Jake L. Greenfield ◽  
Daniele Di Nuzzo ◽  
Emrys Evans ◽  
Satyaprasad P. Senanayak ◽  
Sam Schott ◽  
...  
Keyword(s):  
Self Assembly ◽  
Double Helix ◽  
Mixed Valence ◽  
Fold Increase ◽  
Electrical Current ◽  
Structural Rearrangement ◽  
Molecular Wires ◽  
Coordination Geometry ◽  
Valence Structure ◽  
High Level

<div>Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here we use a bottom-up approach to demonstrate resistive</div><div>switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When we expose the material to an electric field, we determine that approximately 25% of the copper atoms oxidise from Cu(I) to Cu(II) without rupture of the polymer chain. The ability to sustain such high level of oxidation is unprecedented in a copper-based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by Cu(II).</div><div>This mixed-valence structure exhibits a 10<sup>4</sup>-fold increase in</div><div>conductivity, which is projected to last over 10 years. We explain the increase in conductivity as being promoted by the creation, upon oxidation, of partly filled d<sub>z</sub><sup>2</sup></div><div>orbitals aligned along the mixed-valence copper array; the long-lasting nature of the change in conductivity is due to the structural rearrangement of the double-helix, which poses an energetic barrier to re-reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale.</div>

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.

Correction to From Molecular Wires to Molecular Resistors: TCNE, a Class-III/Class-II Mixed-Valence Chemical Switch

2014 ◽  
Vol 33 (19) ◽  
pp. 5618-5618 ◽  
Author(s):  
Alexandre Burgun ◽  
Benjamin G. Ellis ◽  
Thierry Roisnel ◽  
Brian W. Skelton ◽  
Michael I. Bruce ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Molecular Wires ◽  
Class Ii ◽  
Class Iii

scholarly journals Iron versus Ruthenium: Clarifying the Electronic Differences between Prototypical Mixed-Valence Organometallic Butadiyndiyl Bridged Molecular Wires

2018 ◽  
Vol 37 (9) ◽  
pp. 1432-1445 ◽  
Author(s):  
Simon Gückel ◽  
Josef B. G. Gluyas ◽  
Sarah El-Tarhuni ◽  
Alexandre N. Sobolev ◽  
Mark W. Whiteley ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Molecular Wires

Effect of tertiary aliphatic amines on self-assembly of TCNQ in mixed-valence state

2013 ◽  
Vol 20 (1) ◽  
pp. 1-14 ◽  
Author(s):  
Kazunori Hayakawa ◽  
Yukiko Tsuji ◽  
Kensuke Naka
Keyword(s):  
Self Assembly ◽  
Valence State ◽  
Mixed Valence ◽  
Aliphatic Amines ◽  
Mixed Valence State

scholarly journals Face-to-Face Dimeric Tetrathiafulvalenes and Their Cation Radical and Dication Species as Models of Mixed Valence and π-Dimer States

2012 ◽  
Vol 85 (1) ◽  
pp. 51-60 ◽  
Author(s):  
Masashi Hasegawa ◽  
Kota Daigoku ◽  
Kenro Hashimoto ◽  
Hiroyuki Nishikawa ◽  
Masahiko Iyoda
Keyword(s):  
Mixed Valence ◽  
Cation Radical ◽  
Face To Face

CHEMICALLY SELF-ASSEMBLED NANOELECTRONIC COMPUTING NETWORKS

1998 ◽  
Vol 09 (01) ◽  
pp. 1-35 ◽  
Author(s):  
S. BANDYOPADHYAY ◽  
V. P. ROYCHOWDHURY ◽  
D. B. JANES
Keyword(s):  
Self Assembly ◽  
Organic Molecules ◽  
Fault Tolerant ◽  
Molecular Wires ◽  
Logic Circuits ◽  
Boolean Logic ◽  
Computing Machinery ◽  
Self Organized ◽  
Processing Activity ◽  
Image Processors

Recent advances in chemical self-assembly will soon make it possible to synthesize extremely powerful computing machinery from metallic clusters and organic molecules. These self-organized networks can function as Boolean logic circuits, associative memory, image processors, and combinatorial optimizers. Computational or signal processing activity is elicited from simple charge interactions between clusters which are resistively/capacitively linked by conjugated molecular wires or ribbons. The resulting circuits are massively parallel, fault-tolerant, ultrafast, ultradense and dissipate very little power.

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