Distorted copper(ii) radicals with sterically hindered salens: electronic structure and aerobic oxidation of alcohols.

The sterically hindered salen ligands featuring biphenyl and tetramethyl putrescine linkers were synthesized and chelated to copper. The resulting complexes CuLbp,tBu, CuLbp,OMe, CuLpu,tBu and CuLpu,OMe were structurally characterized, showing a significanty tetrahedrally distorted metal center. The complexes show two reversible oxidation waves in the range 0.2 to 0.8 V vs. Fc+/Fc. A further reduction wave is detected in the range -1.4 to -1.7 V vs. Fc+/Fc. It is reversible for CuLbp,tBu and CuLbp,OMe and assigned to the CuII/CuI redox couple. One-electron oxidation of CuLbp,OMe, CuLpu,tBu and CuLpu,OMe was performed chemically and electrochemically. It is accompanied by a quenching of the EPR resonances. Phenoxyl radical formation was established by X-Ray diffraction on the cations [CuLbp,OMe]+ and [CuLpu,OMe]+, whereby the coordination sphere is elongated upon oxidation with quinoidal distributions of bond distances. The cations exhibit a NIR band of moderate intensity in their optical spectrum, supporting their classification as class II mixed-valent radical species according to the Robin Day classification. The proposed electronic structures are supported by DFT calculations. The cations [CuLbp,OMe]+, [CuLpu,tBu]+ and [CuLpu,OMe]+ were active towards aerobic oxidation of the unactivated alcohol 2-phenylethanol, with TON numbers up to 58 within 3 h.

Structural and spectroscopic investigations of nine-coordinate redox active lanthanide complexes with a pincer O,N,O ligand.

The lanthanide complexes EuL3, GdL3, YbL3 and LuL3 of the N,N'-bis(2-hydroxy-di-3,5-tert-butylphenyl)amine were prepared. The X-Ray crystal structures of GdL3 and LuL3 demonstrated a nine-coordinate sphere with three ligand molecules under their anionic diamagnetic form (Cat-N-BQ)-. The complexes showed three oxidation events (Eox11/2 = 0.15-0.16 V, E1/22 = 0.51-55 V, and E1/23 = 0.75-0.78 V vs. Fc+/Fc) via cyclic voltammetry, corresponding to the successive oxidation of the aminophenolate moeities to iminosemiquinone species. The complexes GdL3 and YbL3 were characterized by EPR spectroscopy, allowing for the determination of the zero field splitting (ZFS) parameters in the first case. The monocations (LnL3)+ and monoanions (LnL3)- were electrochemically generated (Ln = Eu, Gd, Yb, Lu), as well as the dications YbL32+ and LuL32+. The spins are antiferromagnetically exchange coupled in the diradical species LuL32+ (|D| = 260 MHz, E = 0). All the complexes (incl. neutral) possess a strong absorption band in the NIR region (730-840 nm, ε > 19 mM-1 cm-1) corresponding to ligand-based transitions.

A redox active switch for lanthanide luminescence in phenolate complexes.

The reversible oxidation of coordinated phenolates into phenoxyl radicals results in a dramatic quenching (>95%) of the luminescence of the f metal ion.

Spin interaction in octahedral zinc complexes of mono- and diradical Schiff and mannich bases.

The four Schiff bases 2-tert-butyl-4-methoxy-6-[(pyridin-2-ylmethylimino)methyl]phenol, 2,4-di-tert-butyl-6-[(pyridin-2-ylmethylimino)methyl]phenol, 2-tert-butyl-4-methoxy-6-(quinolin-8-yliminomethyl)phenol, and 2,4-di-tert-butyl-6-(quinolin-8-yliminomethyl)phenol) as well as one Mannich base, N,N',N,N'-bis[(2-hydroxy-3,5-di-tert-butylbenzyl)(2-pyridylmethyl)]ethylenediamine, and their zinc bis-phenolate complexes 1-5, respectively, have been prepared. The complexes 4 and 5 have been characterized by X-ray diffraction crystallography, showing a zinc ion within an octahedral environment, with a cis orientation of the phenolate moieties. 1-5 exhibit in their cyclic voltammetry curves two anodic reversible waves attributable to the successive oxidation of the phenolates into phenoxyl radicals. Bulk electrolysis at ca. +0.1 V affords the zinc-coordinated monophenoxyl radical species (1(*))(+)-(5(*))(+) characterized by UV-vis absorption bands at 400-440 nm. The more stable radicals are (3(*))(+) and (4(*))(+) (half-life higher than 90 min at 298 K), likely due to the increased charge delocalization within the quinoline moieties. These species exhibit a significant additional near-IR band (epsilon > 1650 M(-1) cm(-1)) attributed to a CT transition. In the two-electron-oxidized species (1(**))(2+)-(5(**))(2+) the radical spins present a weak magnetic coupling. EPR reveals an antiferromagnetic exchange interaction for (1(**))(2+)-(4(**))(2+), whereas an unusual ferromagnetic exchange coupling is operative in (5(**))(2+). The weak magnitude of experimental |J| values (within the 1-5 cm(-1) range) as well as their sign could be well reproduced by DFT calculations at the B3LYP level. The small energy gap between the ground and the first excited spin states allows us to investigate the zero-field splitting (ZFS) of the triplet by EPR spectroscopy. This parameter is found to be axial for all systems, with |D| values of 0.0163 cm(-1) for (1(**))(2+), 0.0182 cm(-1) for (2(**))(2+), 0.0144 cm(-1) for (3(**))(2+), 0.0160 cm(-1) for (4(**))(2+), and 0.0115 cm(-1) for (5(**))(2+). The trend between experimental ZFS is confirmed by DFT calculations, which give further insight regarding its sign (negative for all the compounds). Lower ZFS values are obtained for (2(**))(2+) compared to (1(**))(2+) (and also for (4(**))(2+) compared to (3(**))(2+)), which can be interpreted by an increased delocalization of the spin density over the methoxy para substituent. Significant spin population on the quinoline also contributes to a lowering of the |D| value, as observed when (3(**))(2+) is compared to (1(**))(2+) (and also when (4(**))(2+) is compared to (2(**))(2+)).