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

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dc.contributor.authorWallace AJ
dc.contributor.authorCrittenden, Deborah
dc.contributor.authorWilliamson, Bryce
dc.date.accessioned2023-03-16T22:50:20Z
dc.date.available2023-03-16T22:50:20Z
dc.date.issued2016en
dc.date.updated2023-02-13T02:11:08Z
dc.description.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.en
dc.identifier.citationWallace 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.en
dc.identifier.doihttp://doi.org/10.1139/cjc-2016-0264
dc.identifier.issn0008-4042
dc.identifier.issn1480-3291
dc.identifier.urihttps://hdl.handle.net/10092/105242
dc.languageen
dc.language.isoenen
dc.publisherCanadian Science Publishingen
dc.rightsAll rights reserved unless otherwise stateden
dc.rights.urihttp://hdl.handle.net/10092/17651en
dc.subjectligand field theoryen
dc.subjectCASSCFen
dc.subjectMRMP2en
dc.subjectphthalocyanineen
dc.subjectmultireferenceen
dc.subject.anzsrc03 Chemical Sciencesen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3405 - Organic chemistry::340505 - Physical organic chemistryen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3402 - Inorganic chemistry::340209 - Organometallic chemistryen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3407 - Theoretical and computational chemistry::340701 - Computational chemistryen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3406 - Physical chemistry::340604 - Electrochemistryen
dc.titleCASSCF-based explicit ligand field models clarify the ground state electronic structures of transition metal phthalocyanines (MPc; M = Mn, Fe, Co, Ni, Cu, Zn)en
dc.typeJournal Articleen
uc.collegeFaculty of Science
uc.departmentSchool of Physical & Chemical Sciences
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