Jahn–Teller Distortions of Metal Phthalocyanine Anions [M{sup IV}OPc]{sup n–} (M = Ti, V)

Journal Article · Sat Jun 15 04:00:00 EDT 2019 · Journal of Experimental and Theoretical Physics

DOI:https://doi.org/10.1134/S1063776119050133· OSTI ID:22917731

Khasanov, S. S.; Meletov, K. P.; Shibaeva, R. P. ^[1]

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1. Institute of Solid State Physics, Russian Academy of Sciences (Russian Federation)

Based on X-ray diffraction data, a comparative analysis of the molecular geometry of eight phthalocyanine anions [Ti{sup IV}OPc]{sup n–}, [V{sup IV}OPc]{sup n–} (n = 1, 2) and neutral phthalocyanines [Ti{sup IV}OPc] and [V{sup IV}OPc] is carried out to study Jahn–Teller distortions of their molecular structure. It is experimentally shown that the occupation of a doubly degenerate lowest unoccupied molecular orbital of the [M{sup IV}OPc] molecule level by additional electrons leads to core tetragonal symmetry lowering from C{sub 4v} to C{sub 2v} with a significant change in the bond lengths distribution in the molecule. The effect manifests itself to a greater extent in imine bonds of the C–N{sub im}–C fragment, in which a systemic alternation of bonds into short and long is observed. The degree of distortion is proportional to the charge of the metal phthalocyanine macrocycle of the organic part of the molecule, C{sub 32}H{sub 16}N{sub 8}. The Jahn–Teller distortions of the macrocycle noticeably affect the position of frequencies characteristic of [M{sup IV}OPc] in the Raman spectra of single crystals of anionic phthalocyanine complexes in the range 1100–1700 cm{sup –1}. The experimental patterns agree fairly well with the results of DFT calculations.

• OSTI ID: 22917731
• Journal Information: Journal of Experimental and Theoretical Physics, Journal Name: Journal of Experimental and Theoretical Physics Journal Issue: 6 Vol. 128; ISSN JTPHES; ISSN 1063-7761
• Country of Publication: United States
• Language: English

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ANIONS
DISTRIBUTION
JAHN-TELLER EFFECT
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
MOLECULES
MONOCRYSTALS
PHTHALOCYANINES
RAMAN SPECTRA
SYMMETRY
TITANIUM COMPLEXES
VANADIUM COMPOUNDS
X-RAY DIFFRACTION