The combination of lanthanoid nitrates with 18-crown-6 (18-c-6) and tetrahalocatecholate (X Cat , X=Cl, Br) ligands has afforded two compound series [Ln(18-c-6)(X Cat)(NO )]⋅MeCN (X=Cl, 1-Ln; X=Br, 2-Ln; Ln=La, Ce, Nd, Gd, Tb, Dy). The 18-c-6 ligands occupy equatorial positions of a distorted sphenocorona geometry, whereas the charged ligands occupy the axial positions. The analogues of both series with Ln=Ce, Nd, Tb and Dy exhibit out-of-phase ac magnetic susceptibility signals in the presence of an applied magnetic field, indicative of slow magnetization relaxation. When diluted into a diamagnetic La host to reduce dipolar interactions, the Dy analogue exhibits slow relaxation up to 20 K in the absence of an applied dc field. Concerted magnetic measurements, EPR spectroscopy, and ab initio calculations have allowed elucidation of the mechanisms responsible for slow magnetic relaxation. A consistent approach has been applied to quantitatively model the relaxation data for different lanthanoid analogues, suggesting that the spin dynamics are governed by Raman processes at higher temperatures, transitioning to a dominant phonon bottleneck process as the temperature is decreased, with an observed T rather than the usual T dependence (T is temperature). This anomalous thermal dependence of the phonon bottleneck relaxation is consistent with anharmonic effects in the lattice dynamics, which was predicted by Van Vleck more than 70 years ago.

Variation of alkyl substituents on pyridinophane ancillary ligands governs temperature-dependent valence tautomeric or spin crossover equilibria in a family of cobalt–dioxolene complexes.

A high-temperature, microwave synthesis of [Ru(qpy)3](2+) (qpy = 4,4':2',2'':4'',4'''-quaterpyridine) affords the photosensitiser in quantitative yield. The complex produces H2 photocatalytically in a range extending from the UV region of the spectrum to the red with greater efficiency when compared to [Ru(bpy)3](2+).

Since the initial report by Lehn et al. in 1979, ruthenium tris(bipyridine) ([Ru(bpy) 3 ] 2+ ) and its numerous derivatives were applied as photosensitizers (PSs) in a large panel of photocatalytic conditions while the bis(terpyridine) analogues were disregarded because of their low quantum yields and short excited-state lifetimes. In this study, we prepared a new terpyridine ligand, 4′-(4-bromophenyl)-4,4‴:4″,4‴′-dipyridinyl-2,2′:6′,2″-terpyridine (Bipytpy) and used it to prepare the heteroleptic complex [Ru(Tolyltpy)(Bipytpy)](PF 6 ) 2 (1; Tolyltpy = 4′tolyl-2,2′:6′,2′-terpyridine). Complex 1 exhibits enhanced photophysical properties with a higher quantum yield (7.4 × 10 -4 ) and a longer excited-state lifetime (3.8 ns) compared to those of [Ru(Tolyltpy) 2 ](PF 6 ) 2 (3 × 10 -5 and 0.74 ns, respectively). These enhanced photophysical characteristics and the potential for PS-catalyst interaction through the peripheral pyridines led us to apply the complex for visible-light-driven hydrogen evolution.The photocatalytic system based on 1 as the PS, triethanolamine as a sacrificial donor, and cobaloxime as a catalyst exhibits sustained activity over more than 10 days under blue-light irradiation (light-emitting diode centered at 450 nm). A maximum turnover number of 764 was obtained after 12 days.