Microcrystals engineering using assemblies of di-protonated meso-tetraphenylporphine dimers under Zundel cations operation

Intermolecular Interactions Required for the Formation of Liquid Microcrystals Produced by the Precursors Self-Organized from Protonated TPP Dimers

“…With ω = 2680 cm −1 of the three-peaked band characterizing proton sharing depicted in Figure 2, inset (below) the calculated RO-O = 2.54 Å that is close to 2.56 Å found earlier for the N-O distance in the N-H---O moiety of the protonated water cluster embedded between TPP units in the dimer [7]. The three-component complex is also formed in the presence of hydrochloric acid, the lusterless spot of which is proved very hygroscopic.…”

“…On the solid CaF2 plate, the bands of water confined in the assemblies of the TPP dimers are strongly narrowed in comparison with those on liquid support of oil. This effect has been discussed earlier [12] and it should be noted that the amplitude of the vibrations in the quasi-crystal structure are strongly restricted, while proton moving through the confined water can take place most likely in both cases because the structure self-organization occurs on the solid support too [6,7]. Thus, the proton sharing that takes place in the complex involving THF and CO2 dissolved in water provides the intermolecular interactions required for the formation of liquid microcrystals.…”

“…Among the organic solvents such as dioxane, dimethylformamide, tetrahydrofuran (THF), and acetic acid, the IR spectra of THF containing water were found the most interesting, thin layers of which exhibit three-peaked bands around 2344, 2680, and 3508 cm −1 shown in Figure 1. Obviously the band at 2344 cm -1 testifies the presence of atmospheric CO2 dissolved in water, the other at 3508 cm -1 characterize O-H stretching vibrations, and the band at 2680 cm -1 is the evidence of proton sharing in the O---H + -O moiety [7]. As known, CO2 dissolved in water can produce H + and (HCO3) -.…”

“…Resonance Raman spectrum of meso-tetraphenylporphine dimers, (TPPH)2 2+ that exhibits λmax = 437 nm in 50% aqueous acetone (v/v) (λex = 441.6 nm, a spectral slit width for the registration was 4 cm -1 , He-Cd laser [12]); blue lines show the width at the half of the height and red shows baseline. Inset shows the illustration of proton motions in the N-H3O + ---O moiety of the protonated water cluster embedded between TPP units in the dimer [7].…”

“…The latter mode seems to be very perspective because the engineering of liquid nanocrystals is possible too that may be depending on the physical nature of liquid crystal formation. Such nanocrystals are very likely found in thin layer earlier [7]. In this connection, the physical nature of the formation of liquid crystals, micro-and nano-crystals acquires important significance for future development of the research field.…”