Novel tetrapodal molecules and reticular polyamides based on tetraphenylmethane

Abstract

A series of tetrapodal derivatives of tetraphenylmethane were synthesized and characterized. Crystals obtained from tetrakis(4-acetamidophenyl)methane (lc) and from tetrakis[4-(4-aminobenzamido)phenyl]methane (2b) were analyzed by X-ray diffraction. The analyses pointed to the crystal packing problems faced by molecules of this kind by showing that the crystals, with composition lc'2DMF'2H20 and 2b'2DMSO, respectively, contained cocrystallized solvent molecules. The solvent molecules were found in both cases to be held in place by H bonds; in the case of 2b.2DMSO they occupied channels running along the b axis. Tetrakis(4-aminophenyl)methane (lb) was used in polycondensation reactions with terephthalic acid, under modified Yamazaki conditions, to produce rigid aromatic polyamide networks. The networks were obtained as gels encompassing the whole volume of the reaction mixture. The volume of the gels did not vary noticeably upon changing the solvent (1-methyl-2-pyrrolidone) with less polar solvents, but the gels collapsed upon drying. No crystallinity was observed.

Stimuli‐Responsive, Dynamic Supramolecular Organic Frameworks

“…[61,62] The decoration of 4 positions of the four aromatic rings with functional groups capable of forming additional interaction was found to be an effective strategy to increase the molecule-to-molecule distance leading to the formation of porous frameworks. Such tectons have been successfully applied to the preparation of SOFs through the formation of highly oriented hydrogen bonding motifs such as the ones based on 2-pyridone, [63] carboxylic acid, [64] amide [65] aminotriazine [16] and phenol [66] functional groups.…”

Dynamic self-assembly of ions with variable size and charge in solution

“…This expands the mainly ionically driven self-assembly of ionoids with respect to the sizes, topologies and ionic ratios of the directly involved ionic compounds. We replace the large cation 1 4+ with molecular structures that were also used in the creation of tailor-made materials like 4 2+53-55 and 5 4+ , [56][57][58][59][60] and the biological oligoamine spermine 6 4+61 and/or substitute the small dianionic salts 2 2À and 3 2À with dianions of similar structure (7 2À , 8 2À , 9 2À ) and with a larger trianionic chromophore (10 3À ). Based on these modications we use dynamic light scattering (DLS), continuous wave (CW) electron paramagnetic resonance (EPR) spectroscopy, aided by UV-vis and uorescence spectroscopy, to investigate the interplay between chemical nature, size and ionic ratio for developing dynamically formed, persistent structures like highly dened, colloid-like ionic clusters in solution.…”