Jahn–Teller effect as a controlling parameter of structural and electronic properties
https://doi.org/10.18384/2949-5067-2026-1-6-15
Abstract
Aim: to systematize experimental and theoretical data on the Jahn–Teller effect in metallophthalocyanines (MPc) and identify its role as a universal controlling parameter of structural, electronic, and magnetic properties.
Methodology. Results obtained by X–ray diffraction, electron diffraction, scanning tunneling microscopy, Raman spectroscopy, electron paramagnetic resonance, and density functional theory calculations were analyzed. Experimental and theoretical data from international sources are summarized.
Results. It is shown that the formation of [MPc]⁻ anion radicals causes Jahn–Teller deformation of the macrocycle with an amplitude of Rdist ≈ 0.03–0.07 Å. Direct correlations are established between the deformation amplitude and: (1) the activation energy of electrotransport, (2) the mobility of charge carriers, and (3) the selectivity in CO₂/CO electrocatalysis. Potential–induced Jahn–Teller deformation of the CoN₄ center changes the CO adsorption mechanism (linear 0.52 eV → bridge 1.80 eV), providing control of catalytic selectivity without chemical modification of the molecule.
Research implications. The concept of the Jahn–Teller effect as a fundamental mechanism of MPc functionality is formulated. Methods for targeted control of the structural and electronic properties through electrochemical potential, doping, or fluorination are proposed. Several gaps are identified, and methodological approaches to address them are recommended.
Keywords
Supporting agencies: This research was fully supported by a joint Russia-India grant: the Russian Science Foundation, project No. RSF No. 25-49-01022. https://rscf.ru/project/25-49-01022.
About the Authors
D. E. Sunegin
Federal State University of Education
Russian Federation
Russian Federation
Dmitry E. Sunegin – Postgraduate Student, Faculty of Physics and Mathematics
Moscow
V. V. Belyaev
Federal State University of Education; People’s Friendship University of Russia named after Patrice Lumumba
Russian Federation
Russian Federation
Victor V. Belyaev – Dr. Sci. (Engineering), Prof., Principal Scientist, Science Development Department, Prof., Department of Fundamental Physics and Nanotechnology; Prof., Department of Nanotechnologies and Microsystem Technology
Moscow
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