TY - JOUR

T1 - Experimental and Theoretical Study of Electronic Structure of Zinc Phthalocyanines ZnPc and ZnPcF16

AU - Semushkina, G. I.

AU - Mazalov, L. N.

AU - Lavrukhina, S. A.

AU - Gulyaev, R. V.

AU - Klyamer, D. D.

AU - Basova, T. V.

PY - 2020/3/1

Y1 - 2020/3/1

N2 - The electronic structure of zinc phthalocyanines ZnPc and ZnPcF16 is studied by X-ray emission and X-ray photoelectron spectroscopy methods. Experimental and theoretical parameters of the energy spectrum are analyzed along with the partial composition of highest occupied molecular orbitals (HOMOs) of the molecules of these compounds. It is shown that the frontier high-energy region of ZnPc HOMOs consists of 2pπ atomic orbitals (AOs) of nitrogens from non-equivalent groups (Nα, Nβ) and 2pπ orbitals of peripheral carbons (Cβγδ) with the participation of 3d orbitals of zinc which belong to both π (3dyz, 3dz2) and σ (3dxy) types. It is established that fluorine atoms and the central zinc atom in ZnPcF16 interact with each other by forming delocalized π orbitals with the participation of carbon pπ orbitals belonging to α, β, γ, δ groups as well as nitrogen pπ orbitals of α and β groups. The HOMO of ZnPcF16 consists mainly of 2px and 2py AOs of nitrogen (Nα and Nβ) and carbon (Cβ and Cγδ) with a small contribution of the 3dxz, yz orbital of zinc.

AB - The electronic structure of zinc phthalocyanines ZnPc and ZnPcF16 is studied by X-ray emission and X-ray photoelectron spectroscopy methods. Experimental and theoretical parameters of the energy spectrum are analyzed along with the partial composition of highest occupied molecular orbitals (HOMOs) of the molecules of these compounds. It is shown that the frontier high-energy region of ZnPc HOMOs consists of 2pπ atomic orbitals (AOs) of nitrogens from non-equivalent groups (Nα, Nβ) and 2pπ orbitals of peripheral carbons (Cβγδ) with the participation of 3d orbitals of zinc which belong to both π (3dyz, 3dz2) and σ (3dxy) types. It is established that fluorine atoms and the central zinc atom in ZnPcF16 interact with each other by forming delocalized π orbitals with the participation of carbon pπ orbitals belonging to α, β, γ, δ groups as well as nitrogen pπ orbitals of α and β groups. The HOMO of ZnPcF16 consists mainly of 2px and 2py AOs of nitrogen (Nα and Nβ) and carbon (Cβ and Cγδ) with a small contribution of the 3dxz, yz orbital of zinc.

KW - density functional theory

KW - X-ray emission spectroscopy

KW - X-ray photoelectron spectroscopy

KW - zinc phthalocyanines

KW - METAL-PHTHALOCYANINES

KW - PHOTOELECTRON

KW - RAY

KW - COPPER PHTHALOCYANINE

KW - SPECTRA

KW - VALENCE

KW - COBALT

UR - http://www.scopus.com/inward/record.url?scp=85088637928&partnerID=8YFLogxK

U2 - 10.1134/S0022476620030051

DO - 10.1134/S0022476620030051

M3 - Article

AN - SCOPUS:85088637928

VL - 61

SP - 377

EP - 387

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 3

ER -