Journal ArticleDOI
Versatile Coordination of Azocarboxamides: Redox‐Triggered Change of the Chelating Binding Pocket in Ruthenium Complexes
Johannes Klein,Julia Beerhues,David Schweinfurth,Margarethe van der Meer,Martin Gazvoda,Goutam Kumar Lahiri,Janez Košmrlj,Biprajit Sarkar +7 more
Reads0
Chats0
TLDR
The first instance in which a redox-driven change in the complete chelating binding pocket has been observed in a ruthenium complex as well as with azo-based ligands is observed, showing the potential of these versatile azocarboxamide ligands to act as red ox-driven switches with possible relevance to electrocatalysis.Abstract:
Azocarboxamides occupy a special place among azo ligands owing to their versatility for metal coordination. Herein ruthenium complexes with two different azocarboxamide ligands that differ in the presence (or not) of a coordinating pyridyl heterocycle are presented. By making full use of the O,N(amide), N(azo), and N(pyridyl) coordinating sites, the first diruthenium complex that is bridged by an azo ligand containing two different binding pockets was obtained. Moreover, it was conclusively proven that, in the mononuclear complexes, oxidation at the ruthenium center leads to a complete change of coordination at the chelating binding pocket. The complexes were characterized by NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. Additionally, the mechanism of the aforementioned redox-triggered change in the chelating binding pocket and the electronic structures of all the complexes were investigated by a combination of electrochemistry, UV/Vis/NIR/EPR spectroelectrochemistry, and DFT calculations. This is first instance in which a redox-driven change in the complete chelating binding pocket has been observed in a ruthenium complex as well as with azo-based ligands. These results thus show the potential of these versatile azocarboxamide ligands to act as redox-driven switches with possible relevance to electrocatalysis.read more
Citations
More filters
Journal ArticleDOI
Azo-Branched Covalent Organic Framework Thin Films as Active Separators for Superior Sodium-Sulfur Batteries.
TL;DR: In this paper , the authors synthesize thin films of covalent organic frameworks (COFs) with azobenzene side groups branched to the pore walls.
Journal ArticleDOI
Ruthenium complexes of N/O/S based multidentate ligands: Structural diversities and catalysis perspectives
TL;DR: In this article, a review article highlights selected ruthenium complexes supported with a related class of multidentate ligands containing amide, oxalamide, azocarboxamide and acylthiourea functional groups.
Journal ArticleDOI
Smart Covalent Organic Frameworks with Intrapore Azobenzene Groups for Light-Gated Ion Transport
TL;DR: In this article , a light-responsive COF featuring intrapore azobenzene groups for highly efficient and adjustable transport of multivalent ions is proposed, achieving a K+/Al3+ selectivity of above 6000.
Journal ArticleDOI
Iridium Azocarboxamide Complexes: Variable Coordination Modes, C–H Activation, Transfer Hydrogenation Catalysis, and Mechanistic Insights
Shubhadeep Chandra,Ola Kelm,Uta Albold,Arijit Singha Hazari,Damijana Urankar,Janez Košmrlj,Biprajit Sarkar,Biprajit Sarkar +7 more
TL;DR: Azocarboxamides, a special class of azo ligands, display intriguing electronic properties due to their versatile binding modes and coordination flexibility as discussed by the authors, which may have significant im...
Journal ArticleDOI
Experimental insights on catalytic oxidation of 1,6-hexanediol to ɛ-caprolactone over (p-cymene)RuCl2(L) complexes in non-polar media
Pratya Promchana,Kittisak Choojun,Nararak Leesakul,Saowanit Saithong,Kittipong Chainok,Tawan Sooknoi +5 more
TL;DR: In this paper , 1,6-Hexanediol (1-6-HD) oxidation to caprolactone (CL) was investigated using (p-Cymene)RuCl2(L) complexes with phosphine (LP1-P5) and pyridine (LN1-N5) ligands as catalysts.
References
More filters
Journal ArticleDOI
Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
Journal ArticleDOI
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
Journal ArticleDOI
A short history of SHELX
TL;DR: This paper could serve as a general literature citation when one or more of the open-source SH ELX programs (and the Bruker AXS version SHELXTL) are employed in the course of a crystal-structure determination.
Journal ArticleDOI
Density-functional exchange-energy approximation with correct asymptotic behavior.
TL;DR: This work reports a gradient-corrected exchange-energy functional, containing only one parameter, that fits the exact Hartree-Fock exchange energies of a wide variety of atomic systems with remarkable accuracy, surpassing the performance of previous functionals containing two parameters or more.
Journal ArticleDOI
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
TL;DR: The revised DFT-D method is proposed as a general tool for the computation of the dispersion energy in molecules and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems.