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Intermolecular interactions required for the formation of liquid microcrystals produced by the precursors self-organized from protonated TPP dimers
1  Faculty of Biology, Lomonosov Moscow State University


Alexander V. Udal'tsov

Faculty of Biology, Lomonosov Moscow State University, 119899 Moscow, Russia


Precursors of microcrystals produced in thin layer of self-organized protonated meso-tetraphenylporphine dimers have been investigated by electronic absorption and infrared spectroscopy, non-contact AFM/SNOM, and SEM to elucidate the role of water and water-soluble organic solvent in the processes of the liquid microcrystals formation [1]. It has been found that tetrahydrofuran (THF) is the most suitable organic solvent providing proton moving through the aqueous acid solution that is required for the formation of liquid micro-crystals. A band around 3200 cm–1 corresponds to O–O distance ca. 2.63 Å in the O–H+...O moiety that is consistent with the distance providing proton sharing [2]. So that characteristic band at 3207 cm–1 (or a shoulder at 3228 cm–1 in the presence of HCl), which have been found in IR spectra of THF with small amounts of water, is the prerequisite for the proton moving through water-porphyrin matrix. As evidenced earlier the latter generates the self-organization of the structure [3-4] that is needed for the crystallization. According to AFM/SNOM images, submicroscopic particles consisting of 60-nm particles are covered by a layer of tight water. The tight water was found previously under comparison of the non-contact and contact AFM images [5]. Regular surface of the tight water layer observed by non-contact AFM attests about proton moving through water with the change of the moving direction. The angle of the direction change is sharp, 46.2° or 180°– 46.2°=133.8° depending on the forward or backward proton moving. Tracks of the structure self-organization due to the proton moving observed by SEM on the surface of precursors support this view on the structure self-organization. Similar processes of proton moving through the water-porphyrin matrix are suggested for the prolongation of crystallization germ observed by contact AFM. No crystallization has been found for nanoparticles obtained under the self-assembling of protonated TPP dimers in 7-9% (v/v) aqueous dioxane.


[1] A.V. Udal'tsov, J. Crys. Growth. 448 (2016) 6-16.

[2] A.V. Udal'tsov, J. Mol. Spectr. 11 (2017) in press,

[3] A.V. Udal'tsov, A.V. Bolshakova, J.G. Vos, J. Mol. Struct. 1080 (2015), 14-23.

[4] A.V. Udal'tsov, J. Mol. Struct. 1084 (2015) 308-318.

[5] A.V. Udal'tsov, M. Tosaka, G. Kaupp, J. Mol. Struct. 660 (2003) 15-23.

Keywords: Water-porphyrin interaction; proton sharing; precursors of microcrystals; surface structure; AFM/SNOM; SEM.
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