Correction: Reactivity of a pyridinium-substituted dimethyldihydropyrene switch under aerobic conditions: self-sensitized photo-oxygenation and thermal release of singlet oxygen

Correction for 'Reactivity of a pyridinium-substituted dimethyldihydropyrene switch under aerobic conditions: self-sensitized photo-oxygenation and thermal release of singlet oxygen' by Saioa Cobo et al., Chem. Commun., 2015, 51, 13886–13889

Supplementary material for the article: Wang, L.; Zlatar, M.; Vlahović, F.; Demeshko, S.; Philouze, C.; Molton, F.; Gennari, M.; Meyer, F.; Duboc, C.; Gruden, M. Experimental and Theoretical Identification of the Origin of Magnetic Anisotropy in Intermediate Spin Iron(III) Complexes. Chemistry - A European Journal 2018, 24 (20), 5091–5094. https://doi.org/10.1002/chem.201705989

Supplementary material for: [https://doi.org/10.1002/chem.201705989]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2130

A high-valent non heme μ-oxo MnIV dimer generated from a thiolate-bound MnII complex and O2

International audienceThis study deals with the unprecedented reactivity of dinuclear non-heme MnII -thiolate complexes with O2 , which dependent on the protonation state of the initial MnII dimer selectively generates either a di-μ-oxo or μ-oxo-μ-hydroxo MnIV complex. Both dimers have been characterized by different techniques including single-crystal X-ray diffraction and mass spectrometry. Oxygenation reactions carried out with labeled 18 O2 unambiguously show that the oxygen atoms present in the MnIV dimers originate from O2 . Based on experimental observations and DFT calculations, evidence is provided that these MnIV species comproportionate with a MnII precursor to yield μ-oxo and/or μ-hydroxo MnIII dimers. Our work highlights the delicate balance of reaction conditions to control the synthesis of non-heme high-valent μ-oxo and μ-hydroxo Mn species from MnII precursors and O2

Wavelet-Based Linear-Response Time-Dependent Density-Functional Theory

Linear-response time-dependent (TD) density-functional theory (DFT) has been implemented in the pseudopotential wavelet-based electronic structure program BigDFT and results are compared against those obtained with the all-electron Gaussian-type orbital program deMon2k for the calculation of electronic absorption spectra of N2 using the TD local density approximation (LDA). The two programs give comparable excitation energies and absorption spectra once suitably extensive basis sets are used. Convergence of LDA density orbitals and orbital energies to the basis-set limit is significantly faster for BigDFT than for deMon2k. However the number of virtual orbitals used in TD-DFT calculations is a parameter in BigDFT, while all virtual orbitals are included in TD-DFT calculations in deMon2k. As a reality check, we report the x-ray crystal structure and the measured and calculated absorption spectrum (excitation energies and oscillator strengths) of the small organic molecule N-cyclohexyl-2-(4-methoxyphenyl)imidazo[1,2-a]pyridin-3-amine

Synthesis and X-ray Structure of (2R, 3R, 4R, 5R)-3,4,5-Tris-Benzyloxy-2-Benzyloxymethyl-Piperidin-1-ol, the N-Hydroxy-Analogue of 2,3,4,6-Tetra-O-Benzyl-1-Deoxymannojirimycin

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Synthesis of an Electrodeficient Dipyridylbenzene-like Terdentate Ligand: Cyclometallating Ligand for Highly Emitting Iridium(III) and Platinum(II) Complexes

Cyclometallated iridium(III) and platinum(II) complexes are intensely used in optoelectronics for their photophysical properties and ability to convert excitons from singlet to triplet state, thus improving the device efficiency. In this contribution, we report the multi-steps synthesis of an electrodeficient dipyridylbenzene-like terdentate ligand [N^C^N], namely 2′,6′-dimethyl-2,3′:5′,2″-terpyridine (6), with 18% overall yield. Compound 6 has been employed to synthesize two phosphorescent complexes of platinum(II) and iridium(III), namely compounds 7 and 8, respectively. Both complexes have been characterized by NMR and high resolution mass spectrometry, and demonstrate high luminescence quantum yields in a deaerated solution at room temperature, with 18% and 61% for 7 and 8, respectively. If the iridium(III) complex displays similar emission properties to [Ir(dpyx)(ppy)Cl] (dpyx = 3,5-dimethyl-2,6-dipyridylbenzene and ppy = 2- phenylpyridine), the platinum(II) derivative, with λem = 470 nm, is a rare example of a fluorine atom-free blue emitting [N^C^N]PtCl complex

CoIII and CuII complexes of reduced Schiff bases: Generation of phenoxyl radical species

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Co-II, Ni-II, Cu-II and Zn-II complexes of a bipyridine bis-phenol conjugate: Generation and properties of coordinated radical species

Four bis-phenolate complexes [(ZnL)-L-II], [(NiL)-L-II], [(CuL)-L-II] and [(CoL)-L-II] (where [H2L = 2,2'-[2,2'] bipyridinyl-6-yl-bis-4,6-di-tert-butylphenol] have been synthesized. The copper(II) and nickel(II) complexes have been characterized by X-ray diffraction, showing a metal ion within a square planar geometry, slightly distorted towards tetrahedral. The cyclic voltametry (CV) curve of [(ZnL)-L-II] consists of a single bi-electronic reversible wave at 0.06 V vs. Fc/Fc+. The electrochemically generated dication is a diradical species [(ZnL center dot center dot)-L-II](2+) that exhibits the typical phenoxyl pi-pi* band at 395 nm. It is EPR-silent due to magnetic interactions between the phenoxyl moieties. The CV curves of [(NiL)-L-II] and [(CuL)-L-II] exhibit two distinct ligand-centred one-electron oxidation waves. The first one is observed at E-1/2(1) = 0.38 and 0.40 V for the nickel and copper complex, respectively, and corresponds to the formation of M(II)-coordinated phenoxyl radicals. Accordingly, [(NiLS center dot)-L-II](+) exhibits a strong absorption band at 960 nm and an (S = 1/2) EPR signal centred at g(iso) = 2.02. [(CuLS center dot)-L-II](+) is EPR-silent, in agreement with a magnetic coupling between the metal and the radical spin. In contrast with the other complexes, [(CoL)-L-II] was found to react with dioxygen (mostly in the presence of pyridine), giving rise to a stable (S = 1/2) superoxo radical complex [(CoL)-L-III(Py)(O-2(center dot))]. One-electron oxidation of [(CoL)-L-II] at -0.01 V affords a diamagnetic cobalt(III) complex [(CoL)-L-III](+) that is inert towards O-2 binding, whereas two-electron oxidation leads to the paramagnetic phenoxyl radical species [(CoLS)-L-III](+) whose EPR spectrum features an (S = 1/2) signal at giso = 2.00

alpha and beta-Fucopyranosyl oxyamines : key intermediates for the preparation of fucose-containing glycoconjugates by oxime ligation.

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Copper Complexes of the Tetradentate N,N′ ‐Bis(2‐amino‐3,5‐di‐ tert ‐butylphenyl)‐2,2′‐diaminobiphenyl Ligand

Abstract The ligand N,N′‐ bis(2‐amino‐3,5‐di‐ tert ‐butylphenyl)‐2,2′‐diaminobiphenyl was synthesized and coordinated to copper. Complex 1 + was structurally characterized, showing two deprotonated diiminobenzoquinone ligands coordinated to a single Cu(I) center. The paramagnetic complexes 1 and 1 2+ were generated and characterized by EPR and Vis‐NIR spectroscopy. Complex 1 exhibits an isotropic resonance at g=2.00, which is reminiscent of Cu(I) diiminosemiquinone species. The dication 1 2+ exhibits a metal‐based ground spin state and hence is described as a Cu(II) diiminobenzoquinone complex. Both 1 and 1 + show a NIR band (954, 980 nm) of high intensity (>20 mM −1 cm −1 ) assigned to ligand‐based charge transfer transitions