Redox-Active Ligand in Coordination Chemistry

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (31 March 2018) | Viewed by 24964

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Guest Editor
Rennes Institute of Chemical Sciences, University of Rennes 1, 35042 Rennes Cedex, France
Interests: redox-active ligand; lanthanides; coordination chemistry; luminescence; single molecule magnets; spin crossover; chirality; valence tautomerism
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Special Issue Information

Dear Colleagues,

Redox active ligands display reversible redox changes between several stable oxidation states. Coordination complexes, involving redox-active ligands are of interest for applications in a plethora of research areas such as small molecule catalytic transformations, molecular electronics, molecular magnetism or spintronics. The interest for such ligands has been attracting increasing attention over the last decade due to the possibility of observing electron-transfer processes which paves the route to new catalytic reactivity, interesting phenomena, i.e., valence tautomerism, switching of the optical and magnetic properties.

The purpose of this Special Issue is to cover the latest advances on all aspects of the redox-active ligand involved in coordination chemistry through research articles, as well as review contributions from both experimental and theoretical points of view.

Dr. Fabrice Pointillart
Guest Editor

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Keywords

  • Transition metal chemistry
  • Lanthanide and Actinide chemistry
  • Redox-active Ligands
  • Electrochemistry
  • Electron Transfer
  • Electronic Conductivity
  • Magnetic Properties
  • Photo-physical Properties
  • Electrocatalyst

Published Papers (6 papers)

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Research

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13 pages, 4054 KiB  
Article
Homoleptic Lanthanide Complexes Containing a Redox-Active Ligand and the Investigation of Their Electronic and Photophysical Properties
by Robin A. Taylor, Nico M. Bonanno, Mihaela Cibian, Jeetkia Yadav, Harlyn J. Silverstein, Christopher R. Wiebe, Cole Mauws, Alan J. Lough and Martin T. Lemaire
Inorganics 2018, 6(2), 56; https://doi.org/10.3390/inorganics6020056 - 25 May 2018
Cited by 1 | Viewed by 5359
Abstract
Herein, we describe the preparation, characterization and photophysical properties of neutral lanthanide complexes containing a redox-active ligand 1-(2-pyridylazo)-2-phenanthrol (papl). The complexes likely share similar structural features and bear the formulation Ln(papl)3 (Ln(III) = Gd, Dy, Tb), which is [...] Read more.
Herein, we describe the preparation, characterization and photophysical properties of neutral lanthanide complexes containing a redox-active ligand 1-(2-pyridylazo)-2-phenanthrol (papl). The complexes likely share similar structural features and bear the formulation Ln(papl)3 (Ln(III) = Gd, Dy, Tb), which is supported by electrospray ionization mass spectrometry, CHN analysis, FT-IR and UV–Vis spectroscopy. The synthesis and structural properties of a related complex, Ho(qapl)3 (where qapl = 10-(8-quinolylazo)-9-phenanthrol), is also reported. The complexes feature ligand-centered redox activity, similar to other reported transition metal complexes with papl. Variable temperature magnetic susceptibility measurements (DC and AC) suggest typical free-ion magnetism without any slow-relaxation dynamics. The photophysical properties of the ligand and complexes were investigated and the results of emission spectroscopy indicate ligand-centered processes. Full article
(This article belongs to the Special Issue Redox-Active Ligand in Coordination Chemistry)
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11 pages, 2599 KiB  
Article
Synthesis and Characterization of (pyNO)2GaCl: A Redox-Active Gallium Complex
by Jacob M. Kirsh, Audra J. Woodside, Brian C. Manor, Patrick J. Carroll, Paul R. Rablen and Christopher R. Graves
Inorganics 2018, 6(2), 50; https://doi.org/10.3390/inorganics6020050 - 21 May 2018
Cited by 3 | Viewed by 3510
Abstract
We report the synthesis of a gallium complex incorporating redox-active pyridyl nitroxide ligands. The (pyNO)2GaCl complex was prepared in 85% yield via a salt metathesis route and was characterized by 1H and 13C NMR spectroscopies, X-ray diffraction, [...] Read more.
We report the synthesis of a gallium complex incorporating redox-active pyridyl nitroxide ligands. The (pyNO)2GaCl complex was prepared in 85% yield via a salt metathesis route and was characterized by 1H and 13C NMR spectroscopies, X-ray diffraction, and theory. UV–Vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties of the complex, respectively. Our discussion focuses primarily on a comparison of the gallium complex to the corresponding aluminum derivative and shows that although the complexes are very similar, small differences in the electronic structure of the complexes can be correlated to the identity of the metal. Full article
(This article belongs to the Special Issue Redox-Active Ligand in Coordination Chemistry)
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9 pages, 1580 KiB  
Article
Field-Induced Dysprosium Single-Molecule Magnet Involving a Fused o-Semiquinone-Extended-Tetrathiafulvalene-o-Semiquinone Bridging Triad
by Jessica Flores Gonzalez, Olivier Cador, Lahcène Ouahab, Sergey Norkov, Viacheslav Kuropatov and Fabrice Pointillart
Inorganics 2018, 6(2), 45; https://doi.org/10.3390/inorganics6020045 - 3 May 2018
Cited by 7 | Viewed by 3260
Abstract
The reaction between the 2,2′-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate biradical triad (L) and the metallo-precursor [Dy(hfac)3]·2H2O leads to the formation of a one-dimensional coordination polymer with the formula {[Dy(hfac)3(L)]·2C6H14}n ( [...] Read more.
The reaction between the 2,2′-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate biradical triad (L) and the metallo-precursor [Dy(hfac)3]·2H2O leads to the formation of a one-dimensional coordination polymer with the formula {[Dy(hfac)3(L)]·2C6H14}n (1). The X-ray structure reveals that the polymeric structure is formed by the bridging of the Dy(hfac)3 units with the multi-redox triad L. Single-crystal X-ray diffraction and UltraViolet-visible absorption spectroscopy confirm that the triad L in 1 is bound as a direduced, diprotonated form of o-quinone-extended tetrathiafulvalene-o-quinone (Q-exTTF-Q). Alternate Current (AC) measurements highlight a field-induced single-molecule magnet (SMM) behavior with an energy barrier of 20 K, and thus 1 can be described as a one-dimensional assembly of mononuclear SMMs bridged by the L triad. Full article
(This article belongs to the Special Issue Redox-Active Ligand in Coordination Chemistry)
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10 pages, 2563 KiB  
Communication
A M2L2 Redox-Active Metalla-Macrocycle Based on Electron-Rich 9-(1,3-Dithiol-2-ylidene)Fluorene
by Serhii Krykun, Magali Allain, Vincent Carré, Frédéric Aubriet, Zoia Voitenko, Sébastien Goeb and Marc Sallé
Inorganics 2018, 6(2), 44; https://doi.org/10.3390/inorganics6020044 - 3 May 2018
Cited by 10 | Viewed by 3929
Abstract
A redox-active M2L2 metalla-macrocycle is depicted, of which construction has been achieved through coordination driven self-assembly from an electron-rich 9-(1,3-dithiol-2-ylidene)fluorene bis-pyridyl ligand and a cis-blocked square planar palladium complex (Pd(dppf)OTf2, dppf = 1,1′-Bis(diphenylphosphino)ferrocene). The resulting metalla-macrocycle has [...] Read more.
A redox-active M2L2 metalla-macrocycle is depicted, of which construction has been achieved through coordination driven self-assembly from an electron-rich 9-(1,3-dithiol-2-ylidene)fluorene bis-pyridyl ligand and a cis-blocked square planar palladium complex (Pd(dppf)OTf2, dppf = 1,1′-Bis(diphenylphosphino)ferrocene). The resulting metalla-macrocycle has been fully characterized in solution, as well as in the solid state (X-ray crystal structure). Its electronic properties show that both constitutive ligands can be oxidized independently through a one-electron process. Full article
(This article belongs to the Special Issue Redox-Active Ligand in Coordination Chemistry)
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12 pages, 4468 KiB  
Article
Metal (Hg, Pt, Ru) Bisalkynyl Bridge between Tetrathiafulvalene Electrophores and Electronic Interplay
by Morgan Auffray, Antoine Vacher, Thierry Roisnel and Dominique Lorcy
Inorganics 2018, 6(2), 43; https://doi.org/10.3390/inorganics6020043 - 1 May 2018
Cited by 1 | Viewed by 3061
Abstract
A series of metal (Hg, Pt, Ru) bis(alkynyl-tetrathiafulvalene) complexes have been investigated to study the electronic interplay between the metal and the tetrathiafulvalene (TTF), as well as between the two peripheral TTF electrophores along the organometallic bridge. Cyclic voltammetry experiments, together with spectro-electrochemical [...] Read more.
A series of metal (Hg, Pt, Ru) bis(alkynyl-tetrathiafulvalene) complexes have been investigated to study the electronic interplay between the metal and the tetrathiafulvalene (TTF), as well as between the two peripheral TTF electrophores along the organometallic bridge. Cyclic voltammetry experiments, together with spectro-electrochemical investigations, have shown the electronic effect of the metal center through the linker on redox properties of the TTF, as well as the influence of the length of the conjugated organic linker. These data show that the degree of coupling can be modulated from no coupling with mercury to appreciable electronic coupling between different electrophores with ruthenium. Full article
(This article belongs to the Special Issue Redox-Active Ligand in Coordination Chemistry)
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Review

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28 pages, 20366 KiB  
Review
Functionalized o-Quinones: Concepts, Achievements and Prospects
by Konstantin Martyanov and Viacheslav Kuropatov
Inorganics 2018, 6(2), 48; https://doi.org/10.3390/inorganics6020048 - 13 May 2018
Cited by 14 | Viewed by 5315
Abstract
o-Quinones are both well-studied and promising redox-active chelating ligands. There are plenty of interesting effects to be found on o-quinone-derived metallocomplexes, such as photo-thermo mechanical effect in solid phase and in solution, luminescence, SMM properties and so on. A combination o [...] Read more.
o-Quinones are both well-studied and promising redox-active chelating ligands. There are plenty of interesting effects to be found on o-quinone-derived metallocomplexes, such as photo-thermo mechanical effect in solid phase and in solution, luminescence, SMM properties and so on. A combination o-quinone function with an additional coordination site or redox active fragment in the same molecule might sufficiently extend an assembling as well as functional capability of such ligand in complexes. In this paper, the authors focus on o-quinones decorated with additional non-dioxolene chelating coordination site or with electron donor redox active annelated fragments. Full article
(This article belongs to the Special Issue Redox-Active Ligand in Coordination Chemistry)
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