Multi-Center Redox-Active System: Amine–Amine Electronic Coupling through a Cyclometalated Bisruthenium Segment

2013 ◽  
Vol 52 (7) ◽  
pp. 4040-4045 ◽  
Author(s):  
Chang-Jiang Yao ◽  
Yu-Wu Zhong ◽  
Jiannian Yao
Keyword(s):  
Electronic Coupling ◽  
Active System ◽  
Redox Active ◽  
Amine Amine

Supramolecular redox-active system consisting of biomolecule

1997 ◽  
Vol 67 (1-4) ◽  
pp. 293
Author(s):  
T. Hirao ◽  
A. Nomoto ◽  
S. Yamazaki ◽  
T. Moriuchi ◽  
A. Ogawa
Keyword(s):  
Active System ◽  
Redox Active

Amine–Amine Electronic Coupling through a Dibenzo[a,e]pentalene Bridge

2015 ◽  
Vol 18 (2) ◽  
pp. 256-259 ◽  
Author(s):  
Jun-Jian Shen ◽  
Jiang-Yang Shao ◽  
Xiaozhang Zhu ◽  
Yu-Wu Zhong
Keyword(s):  
Electronic Coupling ◽  
Amine Amine

Metal Chelation-Assisted Amine–Amine Electronic Coupling through the 4,4′-Positions of 2,2′-Bipyridine

2015 ◽  
Vol 54 (4) ◽  
pp. 1272-1282 ◽  
Author(s):  
Hai-Jing Nie ◽  
Wen-Wen Yang ◽  
Ren-Hui Zheng ◽  
Qiang Shi ◽  
Hui Chen ◽  
...  
Keyword(s):  
Electronic Coupling ◽  
Metal Chelation ◽  
Amine Amine

Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices

Science ◽  
2013 ◽  
Vol 343 (6166) ◽  
pp. 66-69 ◽  
Author(s):  
A. Alec Talin ◽  
Andrea Centrone ◽  
Alexandra C. Ford ◽  
Michael E. Foster ◽  
Vitalie Stavila ◽  
...  
Keyword(s):  
Thin Film ◽  
Electrical Conductivity ◽  
First Principles ◽  
Metal Organic Framework ◽  
Electronic Devices ◽  
Electronic Coupling ◽  
Guest Molecules ◽  
Redox Active ◽  
Metal Organic ◽  
Thin Film Devices

We report a strategy for realizing tunable electrical conductivity in metal-organic frameworks (MOFs) in which the nanopores are infiltrated with redox-active, conjugated guest molecules. This approach is demonstrated using thin-film devices of the MOF Cu3(BTC)2 (also known as HKUST-1; BTC, benzene-1,3,5-tricarboxylic acid) infiltrated with the molecule 7,7,8,8-tetracyanoquinododimethane (TCNQ). Tunable, air-stable electrical conductivity over six orders of magnitude is achieved, with values as high as 7 siemens per meter. Spectroscopic data and first-principles modeling suggest that the conductivity arises from TCNQ guest molecules bridging the binuclear copper paddlewheels in the framework, leading to strong electronic coupling between the dimeric Cu subunits. These ohmically conducting porous MOFs could have applications in conformal electronic devices, reconfigurable electronics, and sensors.

scholarly journals A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities

Molecules ◽  
2021 ◽  
Vol 26 (17) ◽  
pp. 5232
Author(s):  
Nils Rotthowe ◽  
Michael Linseis ◽  
Lars Vogelsang ◽  
Nicole Orth ◽  
Ivana Ivanović-Burmazović ◽  
...  
Keyword(s):  
Close Contact ◽  
Nir Spectroscopy ◽  
Electronic Coupling ◽  
X Ray Diffraction ◽  
Reaction Conditions ◽  
Redox Active ◽  
Inductive Effects ◽  
Intervalence Charge Transfer ◽  
Metal Organic ◽  
The Individual

Careful optimization of the reaction conditions provided access to the particularly small tetraruthenium macrocycle 2Ru2Ph-Croc, which is composed out of two redox-active divinylphenylene-bridged diruthenium entities {Ru}-1,4-CH=CH-C6H4-CH=CH-{Ru} (Ru2Ph; {Ru} = Ru(CO)Cl(PiPr3)2) and two likewise redox-active and potentially non-innocent croconate linkers. According to single X-ray diffraction analysis, the central cavity of 2Ru2Ph-Croc is shielded by the bulky PiPr3 ligands, which come into close contact. Cyclic voltammetry revealed two pairs of split anodic waves in the weakly ion pairing CH2Cl2/NBu4BArF24 (BArF24 = [B{C6H3(CF3)2-3,5}4]- electrolyte, while the third and fourth waves fall together in CH2Cl2 / NBu4PF6. The various oxidized forms were electrogenerated and scrutinized by IR and UV/Vis/NIR spectroscopy. This allowed us to assign the individual oxidations to the metal-organic Ru2Ph entities within 2Ru2Ph-Croc, while the croconate ligands remain largely uninvolved. The lack of specific NIR bands that could be assigned to intervalence charge transfer (IVCT) in the mono- and trications indicates that these mixed-valent species are strictly charge-localized. 2Ru2Ph-Croc is hence an exemplary case, where stepwise IR band shifts and quite sizable redox splittings between consecutive one-electron oxidations would, on first sight, point to electronic coupling, but are exclusively due to electrostatic and inductive effects. This makes 2Ru2Ph-Croc a true “pretender”.

A delocalized cobaltoviologen with seven reversibly accessible redox states and highly tunable electrochromic behaviour

2020 ◽  
Vol 56 (89) ◽  
pp. 13864-13867
Author(s):  
Iram F. Mansoor ◽  
Derek I. Wozniak ◽  
Yilei Wu ◽  
Mark C. Lipke
Keyword(s):  
Redox Potential ◽  
Electronic Coupling ◽  
Redox Active Ligands ◽  
Electrochromic Properties ◽  
Redox States ◽  
Redox Active

Cobalt was found to mediate strong electronic coupling between two viologen-like redox-active ligands, providing electrochromic properties that are easily tuned by the applied redox potential.

Mixed valence complexes involving MM quadruple bonds (M=Mo or W)

2007 ◽  
Vol 366 (1862) ◽  
pp. 101-112 ◽  
Author(s):  
Malcolm H Chisholm
Keyword(s):  
Mixed Valence ◽  
Electronic Coupling ◽  
Organic Radical ◽  
Radical Anions ◽  
Class Iii ◽  
Mixed Valency ◽  
Bridging Ligand ◽  
Quadruple Bond ◽  
Redox Active ◽  
Quadruple Bonds

The MM quadruple bond of configuration MM σ 2 π 4 δ 2 is redox active and in many ways ideally suited for studies of mixed valency when two or more such centres are linked by a bridging ligand. In this account, the mechanism of electronic coupling is examined for complexes of the type [L 3 M 2 bridgeM 2 L 3 ] 0/+ where L, a pivalate; bridge, a dicarboxylate or related ligand and M, Mo or W. The represented examples allow us to probe electronic factors close to the class II/III border and readily distinguish between electron and hole transfer in the superexchange mechanism. The potential for mixed valence organic radical anions mediated by the M 2 centre is also raised and one specific example of class III behaviour is described.

scholarly journals Redox potentials along the redox-active low-barrier H-bonds in electron transfer pathways

2020 ◽  
Vol 22 (44) ◽  
pp. 25467-25473 ◽  
Author(s):  
Keisuke Saito ◽  
Manoj Mandal ◽  
Hiroshi Ishikita
Keyword(s):  
Electron Transfer ◽  
Proton Transfer ◽  
Redox Potential ◽  
Driving Force ◽  
Electronic Coupling ◽  
Redox Potentials ◽  
Redox Active ◽  
Electron Transfer Pathways

Local proton transfer along redox-active low-barrier H-bonds can alter the driving force or electronic coupling for electron transfer, as the redox potential values depend on the H+ position in low-barrier H-bonds.

scholarly journals A Delocalized Cobaltoviologen with Seven Reversibly Accessible Redox States and Highly Tunable Electrochromic Behaviour

2020 ◽  
Author(s):  
Iram F. Mansoor ◽  
Derek Wozniak ◽  
yilei wu ◽  
Mark C. Lipke
Keyword(s):  
Electronic Properties ◽  
Class Ii ◽  
Electronic Coupling ◽  
Electrochromic Properties ◽  
Redox States ◽  
Redox Active ◽  
Electronic Delocalization ◽  
Terpyridine Ligands

Cobalt(II) mediates electronic coupling between two N-methyl-pyridinium-terpyridine ligands that are related to redox-active N,N-dialkyl-4,4'-bipyridinium dications (viologens). Borderline Class II/III electronic delocalization imparts the cobaltoviologen complex with distinct electronic properties (e.g. 7 accessible redox states) relative to those of viologens, leading to enhanced electrochromic properties.

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