Transition metal complexes containing a ditopic redox active ligand featuring very intense visible absorption bands

Bonanno, Nico M.; Damme, Natasha Van; Lough, Alan J.; Lemaire, Martin T.

doi:10.1016/j.dyepig.2015.08.006

Cited by 8 publications

(4 citation statements)

References 24 publications

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“…The red shift observed for the transitions in the visible region upon the complexation of the lanthanide ions is in line with what has been reported for other papl complexes with divalent transition metal ions [11], as well as for lanthanide complexes with similar azo-type ligands [18]. This effect arises upon coordination, as only the enolate form of the ligand with the azo-type moiety exists with extended conjugation and a characteristic low lying azo-centered π*-orbital, which is also supported by the intense color of the complexes [9,11,16,18]. The electronic spectra of the uncoordinated papl ligand and complexes 1-3 are illustrated in Figure 2.…”

Section: Preparation and Characterization Of Ln(papl) 3 Ln = Gd Tb supporting

confidence: 89%

“…Unlabeled The electronic spectra of the uncoordinated papl ligand and complexes 1-3 are illustrated in Figure 2. For the uncoordinated papl ligand, a keto-enol tautomerization exists (Scheme 2), with the iminoquinone tautomer being the major component, as found for related compounds [16]. In its absorption spectrum, ligand centered π-π* transitions (225-350 nm) are observed, together with a broad band (350-525 nm) with a higher energy shoulder (~400 nm) in the visible region.…”

Section: Preparation and Characterization Of Ln(papl) 3 Ln = Gd Tb mentioning

confidence: 80%

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Homoleptic Lanthanide Complexes Containing a Redox-Active Ligand and the Investigation of Their Electronic and Photophysical Properties

et al. 2018

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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.

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Section: Preparation and Characterization Of Ln(papl) 3 Ln = Gd Tb supporting

confidence: 89%

Section: Preparation and Characterization Of Ln(papl) 3 Ln = Gd Tb mentioning

confidence: 80%

Homoleptic Lanthanide Complexes Containing a Redox-Active Ligand and the Investigation of Their Electronic and Photophysical Properties

et al. 2018

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“…Redox processes using transition metal complexes with organic ligands are the object of constant interest for researchers who develop catalytic systems. − They have also attracted much attention in the creation of redox-triggered molecular switches − and as a basis of many biochemical processes. , Redox processes are met in studies of molecular magnets − and especially frequently in the development of syntheses of heterospin compounds from transition metal complexes with stable organic radicals. − Over the past 20 years, the products that form as a result of redox reactions between nitroxides and transition metals were detected. For example, it was found that a radical can be reduced to the corresponding hydroxylamine and then form the product of cocrystallization of the starting radical and the complex with nitrone .…”

Section: Introductionmentioning

confidence: 99%

Simultaneous Introduction of Two Nitroxides in the Reaction: A New Approach to the Synthesis of Heterospin Complexes

et al. 2017

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A new approach to the synthesis of multispin compounds has been developed, namely, the simultaneous introduction of two different stable nitroxides (nitronyl nitroxide and imino nitroxide) in a reaction with a metal ion. An important characteristic of the new method is that nitronyl nitroxide and imino nitroxide introduced in the reaction with the metal are the products of different series; i.e., the nitronyl nitroxide molecule differs from the imino nitroxide molecule not only in one additional oxygen molecule per molecule but also in another substituent in the side chain of the organic paramagnet. This possibility was demonstrated on the synthesis of multispin compounds [Ni(A)(L)(Piv)(MeOH)], [Ni(L)(A)(Piv)(HO)], [Co(A)(L)(Piv)(MeOH)], and [Co(L)(A)(Piv)], in which L and A differ in the substituent in the phenyl ring. The number of multispin compounds that can be synthesized by the proposed method is almost unlimited. The heterospin complexes of transition metals with coordinated nitronyl nitroxide and imino nitroxide in one molecule contain energy-different exchange interaction channels that differ in both magnitude and sign, as confirmed by the quantum-chemical analysis of exchange channels in [Ni(B)(B)](NO). The series of mixed-radical complexes may include compounds with nontrivial magnetic properties such as [Co(A)(L)(Piv)(MeOH)], which experiences bulk magnetic ordering below 3.5 K.

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“…[20] Redox-active ligands have had a profound impact on coordination chemistry, and made possible reactivities that were previously inaccessible, or prohibitively expensive. They have many uses, including, though certainly not limited to: efficient electrode materials for lithium ion batteries, [21] strong dyes and pigments, [22] and semiconducting nanosheets. [23] Perhaps most notable is the transformative potential of complexes with redox-active ligands in the field of catalysis.…”

Section: Introductionmentioning

confidence: 99%

N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned

Hill,

Boeré

2024

Chemistry A European J

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The synthesis and extensive characterization of nine aryl sulfur diimides (SDIs, Ar‐NSN‐Ar) are presented with a robust computational and experimental investigation of the fundamental properties of these important members of the thiazyl family of compounds, with particular attention paid to their highly tunable electrochemical behaviour. This is the first work to undertake a systematic comparison of the electrochemical profiles of a coherent series of SDIs to demonstrate and quantify the response of their reduction potentials to substituent electron‐donating and ‐withdrawing properties. This effect is found to be not only exceptionally strong, but also correlates very closely with computed orbital energies. Electron paramagnetic resonance spectroscopy is used to determine the nature, localization, and qualitative lifetimes of the radical anions of SDIs. This work also addresses significant misconceptions about physical properties of SDIs. Experimental data and modern computational methods are employed to provide a resolute answer to the long‐standing contention of the solution‐state conformations of SDIs, and to correct historical mistakes in the assignment of infrared spectroscopic data. High‐quality crystal structures of all SDIs in this work showcase the utility of the recently introduced structural refinement software NoSpherA2, enabling full anisotropic refinement of H‐atoms with accurate C‐H bond lengths.

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Transition metal complexes containing a ditopic redox active ligand featuring very intense visible absorption bands

Cited by 8 publications

References 24 publications

Homoleptic Lanthanide Complexes Containing a Redox-Active Ligand and the Investigation of Their Electronic and Photophysical Properties

Homoleptic Lanthanide Complexes Containing a Redox-Active Ligand and the Investigation of Their Electronic and Photophysical Properties

Simultaneous Introduction of Two Nitroxides in the Reaction: A New Approach to the Synthesis of Heterospin Complexes

N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned

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