One‐Pot Synthesis of Contracted and Expanded Porphyrins with meso‐CF3 Groups

Corrole and sapphyrin with the smallest meso‐substituents reported so far were prepared in a one‐pot synthesis that relies on a non‐aldehydic precursor for introducing CF₃ groups. The substantial amounts of products obtained by this facile pathway allowed for the full characterization of 5,10,15‐tris(trifluoromethyl)corrole, the access to a variety of stable chelates thereof and investigations that disclose the unique structural and chemical properties induced by the CF₃ substituents. The novel 5,10,15,20‐tetra(trifluoromethyl)sapphyrin undergoes only single protonation, which according to its crystal structure is stabilized by favorable non‐bonding F/H interaction between the meso‐CF₃ and the inverted pyrrolic NH.     

One-step conversions of a simple corrole into chiral and amphiphilic derivatives

The reactions of phosgene with 5,10,15-tris(pentafluorophenyl)corrole and its gallium(III) complex lead to a novel chiral macrocycle and an amphiphilic corrole, respectively. Both types of molecules were fully characterized by spectroscopy and X-ray crystallography.     

Dispersion of Polymers in Metallic Gallium

This work examines the concept of dispersing polymers in metals. Herein, this was mainly studied with molten gallium, in which 5‐18 wt % of various short‐chain polymers were incorporated and mixed. The nature of the solidified products was examined by using X‐ray diffraction, electron microscopy, UV/Vis, differential scanning calorimetry, and thermal gravimetric analyses. It was found that some polymers can be dispersed as small domains within molten metals to form a heterogeneous solid. The ability to dope Ga with large polymers opens a new avenue to electronic materials.     

The liquid-phase reaction of CCl3 radicals with primary alcohols

The kinetics of gamma-radiation-induced free-radical reactions in carbon tetrachloride solutions of ethanol and n-pentanol were studied in the range of 0.05–0.80M and 25–170°C. The rate constant for the reaction was found as The activation energy is larger by 0.8 kcal/mol than for secondary alcohols, while the A₁ factors are about the same.