Dynamics and Extent of Ligand Exchange Depend on Electronic Charge of Metal Nanoparticles

2002 ◽  
Vol 124 (24) ◽  
pp. 7096-7102 ◽  
Author(s):  
Yang Song ◽  
Royce W. Murray
Keyword(s):  
Metal Nanoparticles ◽  
Ligand Exchange ◽  
Electronic Charge

Chiral metal nanoparticles encapsulated by a chiral phosphine cavitand with the tetrakis-BINAP moiety: their remarkable stability toward ligand exchange and thermal racemization

2016 ◽  
Vol 45 (11) ◽  
pp. 4486-4490 ◽  
Author(s):  
Ryo Nishimura ◽  
Ryo Yasutake ◽  
Shota Yamada ◽  
Koji Sawai ◽  
Kazuki Noura ◽  
...  
Keyword(s):  
Metal Nanoparticles ◽  
Ligand Exchange ◽  
Au Nanoparticles

A chiral phosphine cavitand1induced the formation of chiral metal (Ru, Rh, Pd, Ag, Pt, and Au) nanoparticles (NPs). The ligand1of the chiral metal NPs prevents both thermal racemization and ligand exchange with a thiol.

Separation of fudosteine on an achiral C18column by HPLC with chiral ligand-exchange selectors as mobile phase additives

2008 ◽  
Vol 20 (4) ◽  
pp. 585-594 ◽  
Author(s):  
J. Ma ◽  
J. Cao ◽  
M. J. Ding ◽  
L. H. Yuan ◽  
M. J. Zhai ◽  
...  
Keyword(s):  
Ligand Exchange ◽  
Mobile Phase ◽  
Chiral Ligand ◽  
Mobile Phase Additives ◽  
Chiral Ligand Exchange

Relation Between Local Structure, Electric Dipole and Charge Carrier Dynamics in DHICA Melanin, a Model for Biocompatible Semiconductors

2019 ◽  
Author(s):  
Micaela Matta ◽  
Alessandro Pezzella ◽  
Alessandro Troisi
Keyword(s):  
Electronic Structure ◽  
Degrees Of Freedom ◽  
Structural Model ◽  
Computational Study ◽  
Oxidative Polymerization ◽  
Radical Scavenging ◽  
Charge Carriers ◽  
Electronic Charge ◽  
Polymer Semiconductors ◽  
Synthetic Pigments

<div><div><div><p>Eumelanins are a family of natural and synthetic pigments obtained by oxidative polymerization of their natural precursors: 5,6 dihydroxyindole and its 2-carboxy derivative (DHICA). The simultaneous presence of ionic and electronic charge carriers makes these pigments promising materials for applications in bioelectronics. In this computational study we build a structural model of DHICA melanin considering the interplay between its many degrees of freedom, then we examine the electronic structure of representative oligomers. We find that a non-vanishing dipole along the polymer chain sets this system apart from conventional polymer semiconductors, determining its electronic structure, reactivity toward oxidation and localization of the charge carriers. Our work sheds light on previously unnoticed features of DHICA melanin that not only fit well with its radical scavenging and photoprotective properties, but open new perspectives towards understanding and tuning charge transport in this class of materials.<br></p></div></div></div>

Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazole-2-ylidene Ligands

2020 ◽  
Author(s):  
Matthew Stout ◽  
Brian Skelton ◽  
Alexandre N. Sobolev ◽  
Paolo Raiteri ◽  
Massimiliano Massi ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Ligand Exchange ◽  
Ligand Substitution ◽  
Bidentate Ligand ◽  
The Other ◽  
Ligand Exchange Reaction ◽  
Multiple Products ◽  
Ligand Charge Transfer ◽  
Photochemical Properties

<p>Three Re(I) tricarbonyl complexes, with general formulation Re(N^L)(CO)<sub>3</sub>X (where N^L is a bidentate ligand containing a pyridine functionalized in the position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo) were synthesized and their reactivity explored in terms of solvent-dependent ligand substitution, both in the ground and excited states. When dissolved in acetonitrile, the complexes bound to the thione ligand underwent ligand exchange with the solvent resulting in the formation of Re(NCMe)<sub>2</sub>(CO)<sub>3</sub>X. The exchange was found to be reversible, and the starting complex was reformed upon removal of the solvent. On the other hand, the complexes appeared inert in dichloromethane or acetone. Conversely, the complex bound to the thiazole-2-ylidene ligand did not display any ligand exchange reaction in the dark, but underwent photoactivated ligand substitution when excited to its lowest metal-to-ligand charge transfer manifold. Photolysis of this complex in acetonitrile generated multiple products, including Re(I) tricarbonyl and dicarbonyl solvato-complexes as well as free thiazole-2-ylidene ligand.</p>

Field Effect Modulation of Electrocatalytic Hydrogen Evolution at Back-Gated Two-Dimensional MoS2 Electrodes

2019 ◽  
Author(s):  
Yan Wang ◽  
Sagar Udyavara ◽  
Matthew Neurock ◽  
C. Daniel Frisbie
Keyword(s):  
Electric Field ◽  
Hydrogen Evolution ◽  
Active Sites ◽  
Density Functional ◽  
Electrode Materials ◽  
Density Functional Theory Calculations ◽  
Electronic Charge ◽  
Back Side ◽  
Gate Electrode ◽  
Conventional Manner

<div> <div> <div> <p> </p><div> <div> <div> <p>Electrocatalytic activity for hydrogen evolution at monolayer MoS2 electrodes can be enhanced by the application of an electric field normal to the electrode plane. The electric field is produced by a gate electrode lying underneath the MoS2 and separated from it by a dielectric. Application of a voltage to the back-side gate electrode while sweeping the MoS2 electrochemical potential in a conventional manner in 0.5 M H2SO4 results in up to a 140-mV reduction in overpotential for hydrogen evolution at current densities of 50 mA/cm2. Tafel analysis indicates that the exchange current density is correspondingly improved by a factor of 4 to 0.1 mA/cm2 as gate voltage is increased. Density functional theory calculations support a mechanism in which the higher hydrogen evolution activity is caused by gate-induced electronic charge on Mo metal centers adjacent the S vacancies (the active sites), leading to enhanced Mo-H bond strengths. Overall, our findings indicate that the back-gated working electrode architecture is a convenient and versatile platform for investigating the connection between tunable electronic charge at active sites and overpotential for electrocatalytic processes on ultrathin electrode materials.</p></div></div></div><br><p></p></div></div></div>

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