Electronic structure of tetracoordinate transition-metal complexes. 2. Comparative theoretical ab initio/Hartree-Fock-Slater and UV-photoelectron spectroscopic studies of building blocks for low-dimensional conductors

Glyoximate complexes of palladium(II) and platinum(II)

Santo Di Bella, Maurizio Casarin, Ignazio Fragalá, Gaetano Granozzi, Tobin J Marks

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Abstract

This contribution presents an integrated experimental He I/He II UV photoelectron spectroscopic and theoretical ab initio pseudopotential and first-principles local exchange DV-Xα approach to understanding the electronic structure of the bis(glyoximato) (gly) complexes of Pd(II) and Pt(II). Theoretical results include evaluation of reorganization energies in the ion state to interpret PE spectroscopic data as well as relativistic corrections to account for the effect of the heavy atom in Pt(gly)2. These results provide convincing descriptions of the metal-ligand bonding. The bonding involves almost all of the upper filled molecular orbitals (σ and π) of the ligand cluster. In particular, interactions with orbitals of σ symmetry involve empty ndxy and (n + 1)s metal orbitals and result in an appreciable ligand-to-metal charge transfer. This effect is especially important in the case of the Pt complexes and raises the energies of metal d subshells. Detailed assignments of the UV PE spectra are proposed on the basis of both theoretical results (ΔSCF and TSIE calculations) and He I/He II intensity changes in the PE spectra. The present results argue that charge transport in low-dimensional, partially oxidized [Pd(gly)2]n systems will occur via bands that are significantly ligand π-electron in character (as in Ni(Pc) salts). In contrast, transport in the corresponding [Pt(gly)2]n systems is likely to be via a largely metal-based band structure (as in conductive tetracyanoplatinate salts).

Original languageEnglish
Pages (from-to)3993-4002
Number of pages10
JournalInorganic Chemistry
Volume27
Issue number22
Publication statusPublished - 1988

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Coordination Complexes
Palladium
Photoelectrons
Platinum
Electronic structure
Transition metals
palladium
photoelectrons
platinum
conductors
Metals
transition metals
electronic structure
Ligands
ligands
metals
Charge transfer
Salts
salts
orbitals

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Electronic structure of tetracoordinate transition-metal complexes. 2. Comparative theoretical ab initio/Hartree-Fock-Slater and UV-photoelectron spectroscopic studies of building blocks for low-dimensional conductors: Glyoximate complexes of palladium(II) and platinum(II)",
abstract = "This contribution presents an integrated experimental He I/He II UV photoelectron spectroscopic and theoretical ab initio pseudopotential and first-principles local exchange DV-Xα approach to understanding the electronic structure of the bis(glyoximato) (gly) complexes of Pd(II) and Pt(II). Theoretical results include evaluation of reorganization energies in the ion state to interpret PE spectroscopic data as well as relativistic corrections to account for the effect of the heavy atom in Pt(gly)2. These results provide convincing descriptions of the metal-ligand bonding. The bonding involves almost all of the upper filled molecular orbitals (σ and π) of the ligand cluster. In particular, interactions with orbitals of σ symmetry involve empty ndxy and (n + 1)s metal orbitals and result in an appreciable ligand-to-metal charge transfer. This effect is especially important in the case of the Pt complexes and raises the energies of metal d subshells. Detailed assignments of the UV PE spectra are proposed on the basis of both theoretical results (ΔSCF and TSIE calculations) and He I/He II intensity changes in the PE spectra. The present results argue that charge transport in low-dimensional, partially oxidized [Pd(gly)2+ρ]n systems will occur via bands that are significantly ligand π-electron in character (as in Ni(Pc)+ρ salts). In contrast, transport in the corresponding [Pt(gly)2+ρ]n systems is likely to be via a largely metal-based band structure (as in conductive tetracyanoplatinate salts).",
author = "{Di Bella}, Santo and Maurizio Casarin and Ignazio Fragal{\'a} and Gaetano Granozzi and Marks, {Tobin J}",
year = "1988",
language = "English",
volume = "27",
pages = "3993--4002",
journal = "Inorganic Chemistry",
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publisher = "American Chemical Society",
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TY - JOUR

T1 - Electronic structure of tetracoordinate transition-metal complexes. 2. Comparative theoretical ab initio/Hartree-Fock-Slater and UV-photoelectron spectroscopic studies of building blocks for low-dimensional conductors

T2 - Glyoximate complexes of palladium(II) and platinum(II)

AU - Di Bella, Santo

AU - Casarin, Maurizio

AU - Fragalá, Ignazio

AU - Granozzi, Gaetano

AU - Marks, Tobin J

PY - 1988

Y1 - 1988

N2 - This contribution presents an integrated experimental He I/He II UV photoelectron spectroscopic and theoretical ab initio pseudopotential and first-principles local exchange DV-Xα approach to understanding the electronic structure of the bis(glyoximato) (gly) complexes of Pd(II) and Pt(II). Theoretical results include evaluation of reorganization energies in the ion state to interpret PE spectroscopic data as well as relativistic corrections to account for the effect of the heavy atom in Pt(gly)2. These results provide convincing descriptions of the metal-ligand bonding. The bonding involves almost all of the upper filled molecular orbitals (σ and π) of the ligand cluster. In particular, interactions with orbitals of σ symmetry involve empty ndxy and (n + 1)s metal orbitals and result in an appreciable ligand-to-metal charge transfer. This effect is especially important in the case of the Pt complexes and raises the energies of metal d subshells. Detailed assignments of the UV PE spectra are proposed on the basis of both theoretical results (ΔSCF and TSIE calculations) and He I/He II intensity changes in the PE spectra. The present results argue that charge transport in low-dimensional, partially oxidized [Pd(gly)2+ρ]n systems will occur via bands that are significantly ligand π-electron in character (as in Ni(Pc)+ρ salts). In contrast, transport in the corresponding [Pt(gly)2+ρ]n systems is likely to be via a largely metal-based band structure (as in conductive tetracyanoplatinate salts).

AB - This contribution presents an integrated experimental He I/He II UV photoelectron spectroscopic and theoretical ab initio pseudopotential and first-principles local exchange DV-Xα approach to understanding the electronic structure of the bis(glyoximato) (gly) complexes of Pd(II) and Pt(II). Theoretical results include evaluation of reorganization energies in the ion state to interpret PE spectroscopic data as well as relativistic corrections to account for the effect of the heavy atom in Pt(gly)2. These results provide convincing descriptions of the metal-ligand bonding. The bonding involves almost all of the upper filled molecular orbitals (σ and π) of the ligand cluster. In particular, interactions with orbitals of σ symmetry involve empty ndxy and (n + 1)s metal orbitals and result in an appreciable ligand-to-metal charge transfer. This effect is especially important in the case of the Pt complexes and raises the energies of metal d subshells. Detailed assignments of the UV PE spectra are proposed on the basis of both theoretical results (ΔSCF and TSIE calculations) and He I/He II intensity changes in the PE spectra. The present results argue that charge transport in low-dimensional, partially oxidized [Pd(gly)2+ρ]n systems will occur via bands that are significantly ligand π-electron in character (as in Ni(Pc)+ρ salts). In contrast, transport in the corresponding [Pt(gly)2+ρ]n systems is likely to be via a largely metal-based band structure (as in conductive tetracyanoplatinate salts).

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