Electronic structure of tetracoordinate transition-metal complexes. 5. Comparative theoretical ab initio/Hartree-Fock-Slater and ultraviolet-photoelectron spectroscopic studies of building blocks for low-dimensional conductors. Dibenzo[b,i][1,4,8,11]tetraazacyclotetradecine complexes of nickel(II) and palladium(II)

Maurizio Casarin, Enrico Ciliberto, Santo Di Bella, Antonino Gulino, Ignazio Fragalà, Tobin J Marks

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The electronic structure of the Ni and Pd complexes of the title ligand have been studied by an integrated experimental He I/He II photoelectron spectroscopic as well as theoretical ab initio pseudopotential and first-principles local exchange DV-Xα approach. Theoretical calculations have provided a complete assignment of photoelectron spectra as well as useful information on the peculiarities of the valence electronic system that, in turn, is of relevance in understanding the properties of low-dimensional, partially oxidized, [M(TAA)p+]n systems. Furthermore, similarities and differences between the present complexes and partially oxidized metallophthalocyanines are discussed in terms of the nature of the HOMO and of twisting motion effects upon the valence bandwidths. The present results argue that the charge transport in tetraazaannulene molecular conductors occurs via bands that are predominantly ligand π-electron in character, and that twisting motions (librations) scarcely affect the resistivity.

Original languageEnglish
Pages (from-to)2835-2842
Number of pages8
JournalInorganic Chemistry
Volume31
Issue number13
Publication statusPublished - 1992

Fingerprint

Coordination Complexes
Palladium
twisting
Photoelectrons
Nickel
Electronic structure
Transition metals
palladium
photoelectrons
conductors
transition metals
nickel
electronic structure
Ligands
valence
ligands
libration
pseudopotentials
Charge transfer
bandwidth

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Electronic structure of tetracoordinate transition-metal complexes. 5. Comparative theoretical ab initio/Hartree-Fock-Slater and ultraviolet-photoelectron spectroscopic studies of building blocks for low-dimensional conductors. Dibenzo[b,i][1,4,8,11]tetraazacyclotetradecine complexes of nickel(II) and palladium(II)",
abstract = "The electronic structure of the Ni and Pd complexes of the title ligand have been studied by an integrated experimental He I/He II photoelectron spectroscopic as well as theoretical ab initio pseudopotential and first-principles local exchange DV-Xα approach. Theoretical calculations have provided a complete assignment of photoelectron spectra as well as useful information on the peculiarities of the valence electronic system that, in turn, is of relevance in understanding the properties of low-dimensional, partially oxidized, [M(TAA)p+]n systems. Furthermore, similarities and differences between the present complexes and partially oxidized metallophthalocyanines are discussed in terms of the nature of the HOMO and of twisting motion effects upon the valence bandwidths. The present results argue that the charge transport in tetraazaannulene molecular conductors occurs via bands that are predominantly ligand π-electron in character, and that twisting motions (librations) scarcely affect the resistivity.",
author = "Maurizio Casarin and Enrico Ciliberto and {Di Bella}, Santo and Antonino Gulino and Ignazio Fragal{\`a} and Marks, {Tobin J}",
year = "1992",
language = "English",
volume = "31",
pages = "2835--2842",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "13",

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TY - JOUR

T1 - Electronic structure of tetracoordinate transition-metal complexes. 5. Comparative theoretical ab initio/Hartree-Fock-Slater and ultraviolet-photoelectron spectroscopic studies of building blocks for low-dimensional conductors. Dibenzo[b,i][1,4,8,11]tetraazacyclotetradecine complexes of nickel(II) and palladium(II)

AU - Casarin, Maurizio

AU - Ciliberto, Enrico

AU - Di Bella, Santo

AU - Gulino, Antonino

AU - Fragalà, Ignazio

AU - Marks, Tobin J

PY - 1992

Y1 - 1992

N2 - The electronic structure of the Ni and Pd complexes of the title ligand have been studied by an integrated experimental He I/He II photoelectron spectroscopic as well as theoretical ab initio pseudopotential and first-principles local exchange DV-Xα approach. Theoretical calculations have provided a complete assignment of photoelectron spectra as well as useful information on the peculiarities of the valence electronic system that, in turn, is of relevance in understanding the properties of low-dimensional, partially oxidized, [M(TAA)p+]n systems. Furthermore, similarities and differences between the present complexes and partially oxidized metallophthalocyanines are discussed in terms of the nature of the HOMO and of twisting motion effects upon the valence bandwidths. The present results argue that the charge transport in tetraazaannulene molecular conductors occurs via bands that are predominantly ligand π-electron in character, and that twisting motions (librations) scarcely affect the resistivity.

AB - The electronic structure of the Ni and Pd complexes of the title ligand have been studied by an integrated experimental He I/He II photoelectron spectroscopic as well as theoretical ab initio pseudopotential and first-principles local exchange DV-Xα approach. Theoretical calculations have provided a complete assignment of photoelectron spectra as well as useful information on the peculiarities of the valence electronic system that, in turn, is of relevance in understanding the properties of low-dimensional, partially oxidized, [M(TAA)p+]n systems. Furthermore, similarities and differences between the present complexes and partially oxidized metallophthalocyanines are discussed in terms of the nature of the HOMO and of twisting motion effects upon the valence bandwidths. The present results argue that the charge transport in tetraazaannulene molecular conductors occurs via bands that are predominantly ligand π-electron in character, and that twisting motions (librations) scarcely affect the resistivity.

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JF - Inorganic Chemistry

SN - 0020-1669

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