RESUMEN
The properties of transition-metal complexes and their chemical dynamics can be effectively modified with ligand substitutions, and theory can be a great aid to such molecular engineering. In this paper, we first theoretically explored how substitution with a Cl atom at different positions of the terpyridine ligand affects the electronic structure of the [Fe(terpy)2]2+ complex. We found that besides the substitution at position 4', the next most promising candidate to cause substantial electronic effects is that where the side pyridine ring is substituted at position 5 (ß). Therefore, next, we examined in detail the Fe(II) complexes of the 5-chloro and 5,5â³-dichloro derivatives of terpy, theoretically and experimentally, to reveal how these substitutions modify the ground state properties and the lifetime of the excited quintet state in such complexes. In addition, we extend the investigation to the complexes of the analogously substituted derivatives of 4'-SMe-terpy. The substitution at position(s) 5 (and 5â³) with Cl lowers the energy of the quintet state and increases its lifetime; the results on the 4'-SMe-substituted complexes show similar changes with these two substitutions, verifying that these effects are more or less additive. This study contributes to the enhancement of our molecular engineering toolset for modifying the potential energy landscape of similar complexes.
RESUMEN
The multilayer of approximate structure MgO(100)/[nFe51Rh49(63 Å)/57Fe51Rh49(46 Å)]10 deposited at 200 °C is primarily of paramagnetic A1 phase and is fully converted to the magnetic B2 phase by annealing at 300 °C for 60 min. Subsequent irradiation by 120 keV Ne+ ions turns the thin film completely to the paramagnetic A1 phase. Repeated annealing at 300 °C for 60 min results in 100% magnetic B2 phase, i.e. a process that appears to be reversible at least twice. The A1 â B2 transformation takes place without any plane-perpendicular diffusion while Ne+ irradiation results in significant interlayer mixing.
RESUMEN
The morphologically and compositionally controlled synthesis of coordination polymers and spinel oxides is highly desirable for realizing new advanced nanomaterial functionalities. Here we develop a novel and scalable strategy, containing a "copolymer-co-morphology" conception, to shape-controlled synthesis of various types of Prussian blue analogues (PBAs). Three series of PBAs MyFe1-y[Co(CN)6]0.67·nH2O (MyFe1-y-Co, M = Co, Mn and Zn) with well-controlled morphology have been successfully prepared through this strategy. Using MnyFe1-y-Co PBAs as the model, by increasing the relative content of Mn, flexible modulation of the morphology could be easily realized. In addition, a series of porous MnxFe1.8-xCo1.2O4 nano-dices with well-inherited morphologies and defined cation distribution could be obtained through a simple thermal treatment of the PBAs. All these results demonstrate the good universality of this novel strategy. When evaluated as an electrocatalyst, the octahedral-site Mn(III)/Mn(IV) content in MnxFe1.8-xCo1.2O4, mainly determined by sensitive (57)Fe Mössbauer in combination with X-ray photoelectron spectroscopic techniques, was discovered to be directly correlated with the oxygen reduction/evolution reaction (ORR/OER) activity.
