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    CASSCF-based explicit ligand field models clarify the ground state electronic structures of transition metal phthalocyanines (MPc; M = Mn, Fe, Co, Ni, Cu, Zn) (2016)

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    Type of Content
    Journal Article
    UC Permalink
    https://hdl.handle.net/10092/105242
    
    Publisher's DOI/URI
    http://doi.org/10.1139/cjc-2016-0264
    
    Publisher
    Canadian Science Publishing
    ISSN
    0008-4042
    1480-3291
    Language
    en
    Collections
    • Science: Journal Articles [1156]
    Authors
    Wallace AJ
    Crittenden, Deborah cc
    Williamson, Bryce cc
    show all
    Abstract

    © 2016 Published by NRC Research Press. Multireference electronic structure methods are used to assign ground state electronic configurations for a series of metallophthalocyanines. Ligand orbital occupancies remain constant across the period and are consistent with a formal 2-charge on the ligand. The d electron configurations of some metallophthalocyanines are straightforward and can be unambiguously assigned, (dxy)2(dxz,dyz)2,2(dz2)2(dx2-y2)n, with n = 2, 1, 0, respectively, for ZnPc, CuPc, and NiPc. Controversies over ground state electronic structure assignments for other metallophthalocyanines arise due to multiple complicating factors: accidental near-degeneracies, environmental effects, and different ligand field models used in interpreting experimental spectra. We demonstrate that explicit ligand field models provide more reliable and consistent interpretations of experimental data than implicit, parameterized alternatives. On this basis, we assign gas-phase electronic ground states for MnPc, (dxy)2(dxz,dyz)1,1(dz2)1and CoPc, (dxy)2(dxz,dyz)2,2(dz2)1, and show that the ground state of FePc cannot be resolved to a single state, with two near-degenerate states that are likely spin-orbit coupled: (dxy)2(dxz,dyz)1,1(dz2)2and (dxy)2(dxz,dyz)2,1(dz2)1. Remaining differences between computational predictions and experimental observations are small and may be ascribed primarily to environmental effects but are also partly due to incomplete modelling of electron correlation.

    Citation
    Wallace AJ, Williamson BE, Crittenden DL (2016). CASSCF-based explicit ligand field models clarify the ground state electronic structures of transition metal phthalocyanines (MPc; M = Mn, Fe, Co, Ni, Cu, Zn). Canadian Journal of Chemistry. 94(12). 1163-1168.
    This citation is automatically generated and may be unreliable. Use as a guide only.
    Keywords
    ligand field theory; CASSCF; MRMP2; phthalocyanine; multireference
    ANZSRC Fields of Research
    34 - Chemical sciences::3405 - Organic chemistry::340505 - Physical organic chemistry
    34 - Chemical sciences::3402 - Inorganic chemistry::340209 - Organometallic chemistry
    34 - Chemical sciences::3407 - Theoretical and computational chemistry::340701 - Computational chemistry
    34 - Chemical sciences::3406 - Physical chemistry::340604 - Electrochemistry
    Rights
    All rights reserved unless otherwise stated
    http://hdl.handle.net/10092/17651

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