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

• A destroying of shell around protonated dimers is needed to complete di-protonation.
• Two H5O2+ ions embedded between TPP units change the shape of their assemblies.
• Assemblies of di-protonated TPP dimers looked like rods crystallized in a thin layer.
• The size of these green crystals produced by the assemblies varies within 30–35 μm.

New approach based on the usage of self-organized assemblies of di-protonated meso-tetraphenylporphine (TPP) dimers under Zundel cations action is suggested for the microcrystals engineering. Properties of the assemblies consisting of water and the protonated dimers, as produced in aqueous HCl in the presence of a small concentration of water-soluble organic solvent were investigated by UV–Vis and infrared spectroscopy and atomic force microscopy (AFM) in thin films. The self-organized assemblies consisting of water and di-protonated TPP dimers looked like long rods produced green crystals. These crystals were found by light microscopy. The ordered assembled structures crystallized into thin layers at open air at relative humidity of least 60%. Three acts of the microcrystals engineering actions are needed to obtain the green crystals that are (i) self-assembling of protonated TPP dimers under Zundel cations operation; (ii) generation of pure rod precursor in the di-protonated state and (iii) application of gaseous water to initiate the crystallization in order to Zundel cations action in the surface layer could occur. The size of the green crystals produced by the self-organized assemblies varies within 30–35 μm.

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