Light‐Driven Coordination‐Induced Spin‐State Switching: Rational Design of Photodissociable Ligands

The bistability of spin states (e.g., spin crossover) in bulk materials is well investigated and understood. We recently extended spin‐state switching to isolated molecules at room temperature (light‐driven coordination‐induced spin‐state switching, or LD‐CISSS). Whereas bistability and hysteresis in conventional spin‐crossover materials are caused by cooperative effects in the crystal lattice, spin switching in LD‐CISSS is achieved by reversibly changing the coordination number of a metal complex by means of a photochromic ligand that binds in one configuration but dissociates in the other form. We present mathematical proof that the maximum efficiency in property switching by such a photodissociable ligand (PDL) is only dependent on the ratio of the association constants of both configurations. Rational design by using DFT calculations was applied to develop a photoswitchable ligand with a high switching efficiency. The starting point was a nickel–porphyrin as the transition‐metal complex and 3‐phenylazopyridine as the photodissociable ligand. Calculations and experiments were performed in two iterative steps to find a substitution pattern at the phenylazopyridine ligand that provided optimum performance. Following this strategy, we synthesized an improved photodissociable ligand that binds to the Ni–porphyrin with an association constant that is 5.36 times higher in its trans form than in the cis form. The switching efficiency between the diamagnetic and paramagnetic state is efficient as well (72 % paramagnetic Ni–porphyrin after irradiation at 365 nm, 32 % paramagnetic species after irradiation at 440 nm). Potential applications arise from the fact that the LD‐CISSS approach for the first time allows reversible switching of the magnetic susceptibility of a homogeneous solution. Photoswitchable contrast agents for magnetic resonance imaging and light‐controlled magnetic levitation are conceivable applications.     

Copper(II) complexes with pyridoxal dithiocarbazate and thiosemicarbazone ligands: crystal structure,spectroscopic analysis and cytotoxic activity

Transition Metal Chemistry - The present study reports the synthesis and crystal structures of Cu(II) complexes with pyridoxal S-allyldithiocarbazate (H2L1) and pyridoxal thiosemicarbazones...     

A Lie symmetry approach for the solution of the inverse kinematics problem

In this paper, it is considered the inverse kinematics problem, which is faced from a differential point of view. In particular, it is shown that an asymptotic inverse kinematics can be interpreted as a Lie symmetry of the direct kinematics. A parameterization of all Lie symmetries of the direct kinematics is proposed, and the classical Newton and gradient method are obtained as particular cases.     

Vibrational Spectrum of a Platinum Complex of Piroxicam

The infrared and Raman spectra of a platinum complex of the antiinflammatory drug piroxicam (Pir) and dimethylsulfoxide (DMSO) of composition [PtCl₂Pir(DMSO)] were recorded and briefly discussed on the basis of its structural characteristics. The metal-to-ligand vibrations are analyzed in detail.