Molecular Structure of Nickel Octamethylporphyrin-Rare Experimental Evidence of a Ruffling Effect in Gas Phase

Alexander E Pogonin; Arseniy A Otlyotov; Yury Minenkov; Alexander S Semeikin; Yuriy A Zhabanov; Sergey A Shlykov; Georgiy V Girichev

doi:10.3390/ijms23010320

Molecular Structure of Nickel Octamethylporphyrin-Rare Experimental Evidence of a Ruffling Effect in Gas Phase

Int J Mol Sci. 2021 Dec 28;23(1):320. doi: 10.3390/ijms23010320.

Authors

Alexander E Pogonin¹, Arseniy A Otlyotov^{2

3}, Yury Minenkov^{3

4}, Alexander S Semeikin⁵, Yuriy A Zhabanov², Sergey A Shlykov⁶, Georgiy V Girichev²

Affiliations

¹ Department of Nanomaterials and Ceramic Technology, Ivanovo State University of Chemistry and Technology, Sheremetevsky Avenue 7, 153000 Ivanovo, Russia.
² Department of Physics, Ivanovo State University of Chemistry and Technology, Sheremetevsky Avenue 7, 153000 Ivanovo, Russia.
³ N.N. Semenov Institute of Chemical Physics of Russian Academy of Sciences, Kosygina Street 4, 119991 Moscow, Russia.
⁴ Joint Institute for High Temperatures, Russian Academy of Sciences, 13-2 Izhorskaya Street, 125412 Moscow, Russia.
⁵ Department of Organic Chemistry, Ivanovo State University of Chemistry and Technology, Sheremetevsky Avenue 7, 153000 Ivanovo, Russia.
⁶ Department of Physical and Colloidal Chemistry, Ivanovo State University of Chemistry and Technology, Sheremetevsky Avenue 7, 153000 Ivanovo, Russia.

Abstract

The structure of a free nickel (II) octamethylporphyrin (NiOMP) molecule was determined for the first time through a combined gas-phase electron diffraction (GED) and mass spectrometry (MS) experiment, as well as through quantum chemical (QC) calculations. Density functional theory (DFT) calculations do not provide an unambiguous answer about the planarity or non-planar distortion of the NiOMP skeleton. The GED refinement in such cases is non-trivial. Several approaches to the inverse problem solution were used. The obtained results allow us to argue that the ruffling effect is manifested in the NiOMP molecule. The minimal critical distance between the central atom of the metal and nitrogen atoms of the coordination cavity that provokes ruffling distortion in metal porphyrins is about 1.96 Å.

Keywords: electron diffraction; molecular structure; nickel; porphyrin; quantum chemistry; ruffling distortion.

MeSH terms

Density Functional Theory
Gases / chemistry*
Models, Molecular*
Molecular Conformation
Nickel / chemistry*
Porphyrins / chemistry*
Thermodynamics

Substances

Gases
Porphyrins
Nickel

Abstract

MeSH terms

Substances

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