No abstract

Post-functionalization of porphyrinoid catalysts provides a powerful tool for fine-tuning their electronic structure. We have succeeded in the stepwise methylation of the peripheral nitrogen atoms in ruthenium and cobalt 5,15diazaporphyrins. The axial coordination of an anion to the metal center accelerates the second methylation through charge neutralization. N-Methylation of the diazaporphyrin complexes effectively controls their electron deficiency, Lewis acidity, and catalytic activity.

Fluorination of sp3 C–H bonds has attracted considerable attention as a promising method for the synthesis of organofluorine compounds. Manganese porphyrins have been extensively investigated as catalysts in the fluorination of saturated sp3 C–H bonds. Recently, we have found that iron(III) 5,15-diazaporphyrins, which are porphyrin analogues with imine-type sp2-hybridized nitrogen atoms at the meso-positions, showed high catalytic performance in the oxidation of sp3 C–H bonds. Here we disclose the synthesis, structure, and electronic properties of manganese(III) 5,15-diazaporphyrins. We also demonstrate the catalysis of chloromanganese(III) 5,15-diazaporphyrins for benzylic fluorination.

We prepared a free-base 10,20-diphenyl-5,15-diazaporphyrin and its Ni(II), Cu(II), Pd(II), and Pt(II) complexes. These molecules uniformly form an infinite one-dimensional [Formula: see text]-stacking array in the solid state. The four-fold intermolecular hydrogen bonding interactions between the meso-nitrogen atom of the diazaporphyrin core and the ortho-hydrogen atom of the phenyl substituent dominate the crystal packing arrangement. The present study revealed that the meso-nitrogen atom of diazaporphyrins would be used as an inherent hydrogen bonding acceptor to construct supramolecular assemblies.

This study focused on the odors in elder care environments, as odors are one of the most important issues in long-term care environments. The aim of this report is to clarify the actual condition of home care and how caregivers evaluate the care environment.To achieve this, we conducted a questionnaire survey of caregivers living together with the elderly who use long-term care insurance.The results were as follows 1. More than 70% of the elderly are over 80 years old, and 28% are certified as care level 4 or 5, which means that they require substantial care or support in daily life. A total of 52% of the caregivers take care of the elderly without any support from other family members.2. Irrespective of the care level, home care of the elderly is a burden to the caregiver. Over 60% of the caregivers think that it is difficult to contact their friends, maintain their social life and invite people home.